Barrier metal film production apparatus, barrier metal film production method, metal film production method, and metal film production apparatus

ABSTRACT

A Cl 2  gas plasma is generated at a site within a chamber between a substrate and a metal member. The metal member is etched with the Cl 2  gas plasma to form a precursor. A nitrogen gas is excited in a manner isolated from the chamber accommodating the substrate. A metal nitride is formed upon reaction between excited nitrogen and the precursor, and formed as a film on the substrate. After film formation of the metal nitride, a metal component of the precursor is formed as a film on the metal nitride on the substrate. In this manner, a barrier metal film with excellent burial properties and a very small thickness is produced at a high speed, with diffusion of metal being suppressed and adhesion to the metal being improved.

[0001] The entire disclosures of Japanese Patent Application No.2002-44296 filed on Feb. 21, 2002, Japanese Patent Application No.2002-44289 filed on Feb. 21, 2002, Japanese Patent Application No.2002-027738 filed on Feb. 5, 2002, and Japanese Patent Application No.2001-348325 filed on Nov. 14, 2001, each including specification,claims, drawings and summary, are incorporated herein by reference intheir entirety.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] This invention relates to a production apparatus and a productionmethod for a barrier metal film to be formed on the surface of asubstrate for eliminating the diffusion of a metal into the substrateand retaining the adhesion of the metal, when a metal film is formed onthe surface of the substrate.

[0004] The present invention also relates to a metal film productionmethod and a metal film production apparatus which can form a film of ametal, with the diffusion of the metal being eliminated and the adhesionof the metal being retained, by treating the surface of a barrier metalfilm produced on a substrate.

[0005] 2. Description of Related Art

[0006] Semiconductors with electrical wiring have increasingly usedcopper as a material for the wiring in order to increase the speed ofswitching, decrease transmission loss, and achieve a high density. Inapplying the copper wiring, it has been common practice to perform thevapor phase growth method or plating on a substrate having a depressionfor wiring on its surface, thereby forming a copper film on the surfaceincluding the depression.

[0007] In forming the copper film on the surface of the substrate, abarrier metal film (for example, a nitride of tantalum, tungsten,titanium or silicon) is prepared beforehand on the surface of thesubstrate in order to eliminate the diffusion of copper into thesubstrate, and retain the adhesion of copper. When plating is employed,a copper shielding layer is formed on the barrier metal film by physicalor chemical vapor deposition, and used also as an electrode. The barriermetal film has been formed by physical vapor deposition such assputtering.

[0008] The depression for wiring, formed on the surface of thesubstrate, tends to be decreased in size, and a demand is expressed fora further reduction in the thickness of the barrier metal film. However,the barrier metal film has been produced by use of sputtering, and itsdirectionality is not uniform. With a tiny depression on the surface ofthe substrate, therefore, the film is formed at the entrance of thedepression before being formed in the interior of the depression,resulting in insufficient burial of the depression. Also, the substratehas been badly damaged.

[0009] Additionally, the barrier metal film is prepared for the purposesof preventing the diffusion of copper into the substrate and retainingthe adhesion of copper. Hence, a nitride of tantalum, tungsten ortitanium is formed as a first layer for prevention of copper diffusion,and an active metal, such as tantalum, tungsten or titanium, is formedas a second layer for retention of adhesion to copper. However, thebarrier metal film is so thin that it poses difficulty at the presenttime in performing both functions, the prevention of copper diffusioninto the substrate and the retention of copper adhesion. A demand isgrowing for the advent of a barrier metal film which accomplishes thesetwo functions.

[0010] In particular, the wiring depression formed on the surface of thesubstrate is showing a tendency toward compactness, and further thinningof the barrier metal film is demanded. However, the necessary minimumfilm thickness has increased, if the barrier metal film is constructedin a two-layer structure by forming a nitride of tantalum, tungsten ortitanium as a first layer for prevention of copper diffusion, andforming an active metal, such as tantalum, tungsten or titanium, as asecond layer for retention of adhesion to copper.

SUMMARY OF THE INVENTION

[0011] The present invention has been accomplished in light of thecircumstances described above. An object of the invention is to providea barrier metal film production apparatus and a barrier metal filmproduction method which can form a barrier metal film with excellentburial properties and a very small thickness at a high speed. Anotherobject of the invention is to provide a barrier metal film productionapparatus and a barrier metal film production method which can form abarrier metal film with excellent adhesion to a metal formed as a filmon the surface of the substrate. Still another object of the inventionis to provide a metal film production method and a metal film productionapparatus capable of forming a barrier metal film which, although verythin, prevents diffusion of a metal and retains adhesion to the metal.

[0012] According to the present invention, there is provided a barriermetal film production apparatus, comprising:

[0013] a chamber accommodating a substrate;

[0014] a metallic etched member provided in the chamber at a positionopposed to the substrate;

[0015] source gas supply means for supplying a source gas containing ahalogen to an interior of the chamber between the substrate and theetched member;

[0016] plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas;

[0017] excitation means for exciting a nitrogen-containing gas in amanner isolated from the chamber;

[0018] formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor; and

[0019] control means which makes a temperature of the substrate lowerthan a temperature of the formation means to form the metal nitride as afilm on the substrate.

[0020] Thus, a barrier metal film comprising a film of a metal nitrideand suppressing diffusion can be prepared by forming a metal with theuse of a plasma. The barrier metal film can be formed uniformly to asmall thickness. Consequently, the barrier metal film can be formedhighly accurately at a high speed with excellent burial properties in avery small thickness even to the interior of a tiny depression, forexample several hundred nanometers wide, which has been provided in thesubstrate.

[0021] According to the present invention, there is also provided abarrier metal film production apparatus, comprising:

[0022] a chamber accommodating a substrate;

[0023] a metallic etched member provided in the chamber at a positionopposed to the substrate;

[0024] source gas supply means for supplying a source gas containing ahalogen to an interior of the chamber between the substrate and theetched member;

[0025] plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas;

[0026] excitation means for exciting a nitrogen-containing gas in amanner isolated from the chamber;

[0027] formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor; and

[0028] control means which makes a temperature of the substrate lowerthan a temperature of the formation means to form the metal nitride as afilm on the substrate, and after film formation of the metal nitride,stops supply of the nitrogen-containing gas, and makes the temperatureof the substrate lower than a temperature of the etched member to formthe metal component of the precursor as a film on the metal nitride onthe substrate.

[0029] Thus, a barrier metal film comprising a film of a metal nitrideand a metal film and with diffusion suppressed and adhesion improved canbe prepared by forming a metal by plasmas. The barrier metal film can beformed uniformly to a small thickness. Consequently, the barrier metalfilm can be formed highly accurately at a high speed with excellentburial properties in a very small thickness even to the interior of atiny depression, for example several hundred nanometers wide, which hasbeen provided in the substrate.

[0030] According to the present invention, there is also provided abarrier metal film production apparatus, comprising:

[0031] a chamber accommodating a substrate;

[0032] a metallic etched member provided in the chamber at a positionopposed to the substrate;

[0033] source gas supply means for supplying a source gas containing ahalogen to an interior of the chamber between the substrate and theetched member;

[0034] nitrogen-containing gas supply means for supplying anitrogen-containing gas to an interior of the chamber between thesubstrate and the etched member;

[0035] plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma and anitrogen-containing gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and that a metalnitride is formed upon reaction between nitrogen and the precursor; and

[0036] control means which makes a temperature of the substrate lowerthan a temperature of the etched member to form the metal nitride as afilm on the substrate.

[0037] Thus, a barrier metal film comprising a film of a metal nitrideand a metal film and with diffusion suppressed can be prepared byforming a metal by plasmas. The barrier metal film can be formeduniformly to a small thickness. Also, the supply lines for gases can besimplified, and the number of plasma sources can be decreased, so thatthe product cost can be reduced. Consequently, the barrier metal filmcan be formed highly accurately at a high speed and at a low cost withexcellent burial properties in a very small thickness even to theinterior of a tiny depression, for example several hundred nanometerswide, which has been provided in the substrate.

[0038] According to the present invention, there is also provided abarrier metal film production apparatus, comprising:

[0039] a chamber accommodating a substrate;

[0040] a metallic etched member provided in the chamber at a positionopposed to the substrate;

[0041] source gas supply means for supplying a source gas containing ahalogen to an interior of the chamber between the substrate and theetched member;

[0042] nitrogen-containing gas supply means for supplying anitrogen-containing gas to an interior of the chamber between thesubstrate and the etched member;

[0043] plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma and anitrogen-containing gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and that a metalnitride is formed upon reaction between nitrogen and the precursor; and

[0044] control means which makes a temperature of the substrate lowerthan a temperature of the etched member to form the metal nitride as afilm on the substrate, then stops supply of the nitrogen-containing gas,and makes the temperature of the substrate lower than the temperature ofthe etched member to form the metal component of the precursor as a filmon the metal nitride on the substrate.

[0045] Thus, a barrier metal film comprising a film of a metal nitrideand a metal film and with diffusion suppressed and adhesion improved canbe prepared by forming a metal by plasmas. The barrier metal film can beformed uniformly to a small thickness. Also, the supply lines for gasescan be simplified, and the number of plasma sources can be decreased, sothat the product cost can be reduced. Consequently, the barrier metalfilm can be formed highly accurately at a high speed and at a low costwith excellent burial properties in a very small thickness even to theinterior of a tiny depression, for example several hundred nanometerswide, which has been provided in the substrate.

[0046] According to the present invention, there is also provided abarrier metal film production method comprising:

[0047] supplying a source gas containing a halogen to an interior of achamber between a substrate and a metallic etched member;

[0048] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas;

[0049] exciting a nitrogen-containing gas in a manner isolated from thechamber accommodating the substrate;

[0050] forming a metal nitride upon reaction between excited nitrogenand the precursor; and

[0051] making a temperature of the substrate lower than a temperature ofmeans for formation of the metal nitride to form the metal nitride as afilm on the substrate.

[0052] Thus, a barrier metal film comprising a film of a metal nitrideand suppressing diffusion can be prepared by forming a metal by plasma.The barrier metal film can be formed uniformly to a small thickness.Consequently, the barrier metal film can be formed highly accurately ata high speed with excellent burial properties in a very small thicknesseven to the interior of a tiny depression, for example several hundrednanometers wide, which has been provided in the substrate.

[0053] According to the present invention, there is also provided abarrier metal film production method comprising:

[0054] supplying a source gas containing a halogen to an interior of achamber between a substrate and a metallic etched member;

[0055] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas;

[0056] exciting a nitrogen-containing gas in a manner isolated from thechamber accommodating the substrate;

[0057] forming a metal nitride upon reaction between excited nitrogenand the precursor;

[0058] making a temperature of the substrate lower than a temperature ofmeans for formation of the metal nitride to form the metal nitride as afilm on the substrate; and

[0059] after film formation of the metal nitride, stopping supply of thenitrogen-containing gas, and making the temperature of the substratelower than a temperature of the etched member to form the metalcomponent of the precursor as a film on the metal nitride on thesubstrate.

[0060] Thus, a barrier metal film comprising a film of a metal nitrideand a metal film and with diffusion suppressed and adhesion improved canbe prepared by forming a metal by plasmas. The barrier metal film can beformed uniformly to a small thickness. Consequently, the barrier metalfilm can be formed highly accurately at a high speed with excellentburial properties in a very small thickness even to the interior of atiny depression, for example several hundred nanometers wide, which hasbeen provided in the substrate.

[0061] According to the present invention, there is also provided abarrier metal film production method comprising:

[0062] supplying a source gas containing a halogen and anitrogen-containing gas to an interior of a chamber between a substrateand a metallic etched member;

[0063] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma and a nitrogen-containing gas plasma sothat the etched member is etched with the source gas plasma to form aprecursor from a metal component contained in the etched member and thesource gas, and that a metal nitride is formed upon reaction betweennitrogen and the precursor; and

[0064] making a temperature of the substrate lower than a temperature ofthe etched member to form the metal nitride as a film on the substrate.

[0065] Thus, a barrier metal film comprising a film of a metal nitrideand with diffusion suppressed can be prepared by forming a metal byplasmas. The barrier metal film can be formed uniformly to a smallthickness. Also, the supply line for gases can be simplified, and thenumber of plasma sources can be decreased, so that the product cost canbe reduced. Consequently, the barrier metal film can be formed highlyaccurately at a high speed and at a low cost with excellent burialproperties in a very small thickness even to the interior of a tinydepression, for example several hundred nanometers wide, which has beenprovided in the substrate.

[0066] According to the present invention, there is also provided abarrier metal film production method comprising:

[0067] supplying a source gas containing a halogen and anitrogen-containing gas to an interior of a chamber between a substrateand a metallic etched member;

[0068] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma and a nitrogen-containing gas plasma sothat the etched member is etched with the source gas plasma to form aprecursor from a metal component contained in the etched member and thesource gas, and that a metal nitride is formed upon reaction betweennitrogen and the precursor;

[0069] making a temperature of the substrate lower than a temperature ofthe etched member to form the metal nitride as a film on the substrate;and

[0070] after film formation of the metal nitride, stopping supply of thenitrogen-containing gas, and making the temperature of the substratelower than the temperature of the etched member to form the metalcomponent of the precursor as a film on the metal nitride on thesubstrate.

[0071] Thus, a barrier metal film comprising a film of a metal nitrideand a metal film and with diffusion suppressed and adhesion improved canbe prepared by forming a metal by plasmas. The barrier metal film can beformed uniformly to a small thickness. Also, the supply line for gasescan be simplified, and the number of plasma sources can be decreased, sothat the product cost can be reduced. Consequently, the barrier metalfilm can be formed highly accurately at a high speed and at a low costwith excellent burial properties in a very small thickness even to theinterior of a tiny depression, for example several hundred nanometerswide, which has been provided in the substrate.

[0072] According to the present invention, there is also provided abarrier metal film production apparatus, comprising:

[0073] a chamber accommodating a substrate;

[0074] a metallic etched member provided in the chamber at a positionopposed to the substrate;

[0075] source gas supply means for supplying a source gas containing ahalogen into the chamber;

[0076] nitrogen-containing gas supply means for supplying a gascontaining nitrogen into the chamber;

[0077] plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas, andwhich converts the atmosphere within the chamber into a plasma togenerate a nitrogen-containing gas plasma so that a metal nitride isformed upon reaction between nitrogen and the precursor;

[0078] control means which makes a temperature of the substrate lowerthan a temperature of the plasma generation means to form the metalnitride as a barrier metal film on a surface of the substrate;

[0079] diluent gas supply means for supplying a diluent gas to a siteabove the surface of the substrate; and

[0080] surface treatment plasma generation means for performing asurface treatment which converts the atmosphere within the chamber intoa plasma to generate a diluent gas plasma so that nitrogen atoms in asuperficial layer of the barrier metal film are removed by the diluentgas plasma to decrease a nitrogen content of the superficial layerrelative to an interior of a matrix of the barrier metal film.

[0081] Thus, a barrier metal film comprising a metal nitride layer and ametal layer can be prepared without the increase of the film thickness.Consequently, a barrier metal film production apparatus can be achievedwhich is capable of forming a barrier metal film at a high speed withexcellent burial properties in a very small thickness, and also forminga barrier metal film with excellent adhesion to a metal formed as a filmon the surface of the barrier metal film.

[0082] The barrier metal film production apparatus may further compriseoxygen gas supply means for supplying an oxygen gas into the chamberimmediately before formation of the most superficial layer of thebarrier metal film is completed; and oxygen plasma generation meanswhich converts the atmosphere within the chamber into a plasma togenerate an oxygen gas plasma so that an oxide layer is formed on themost superficial layer of the barrier metal film.

[0083] Thus, because of an oxide layer, if a metal is deposited on thesurface of the barrier metal film, wettability by the metal can berendered satisfactory, thus increasing adhesion.

[0084] According to the present invention, there is also provided abarrier metal film production apparatus, comprising:

[0085] a chamber accommodating a substrate;

[0086] a metallic etched member provided in the chamber at a positionopposed to the substrate;

[0087] source gas supply means for supplying a source gas containing ahalogen into the chamber;

[0088] nitrogen-containing gas supply means for supplying a gascontaining nitrogen into the chamber;

[0089] plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas, andwhich converts the atmosphere within the chamber into a plasma togenerate a nitrogen-containing gas plasma so that a metal nitride isformed upon reaction between nitrogen and the precursor;

[0090] control means which makes a temperature of the substrate lowerthan a temperature of the plasma generation means to form the metalnitride as a barrier metal film on a surface of the substrate;

[0091] oxygen gas supply means for supplying an oxygen gas to a siteabove the surface of the substrate; and

[0092] oxygen plasma generation means for performing a surface treatmentwhich converts the atmosphere within the chamber into a plasma togenerate an oxygen gas plasma so that nitrogen atoms in a superficiallayer of the barrier metal film are removed by the oxygen gas plasma todecrease a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film, and at the same time,forming an oxide layer on the most superficial layer of the barriermetal film.

[0093] Thus, a barrier metal film comprising a metal nitride layer and ametal layer can be prepared with a minimum nozzle construction withoutthe increase of the film thickness, and an oxide layer givessatisfactory wettability by a metal deposited on the surface of thebarrier metal film. Consequently, a barrier metal film productionapparatus can be achieved which is capable of forming a barrier metalfilm at a high speed with excellent burial properties in a very smallthickness, and also forming a barrier metal film with excellent adhesionto a metal formed as a film on the surface of the barrier metal film.

[0094] According to the present invention, there is also provided abarrier metal film production apparatus, comprising:

[0095] a chamber accommodating a substrate;

[0096] a metallic etched member provided in the chamber at a positionopposed to the substrate;

[0097] source gas supply means for supplying a source gas containing ahalogen into the chamber;

[0098] nitrogen-containing gas supply means for supplying a gascontaining nitrogen into the chamber;

[0099] plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas, andwhich converts the atmosphere within the chamber into a plasma togenerate a nitrogen-containing gas plasma so that a metal nitride isformed upon reaction between nitrogen and the precursor;

[0100] control means which makes a temperature of the substrate lowerthan a temperature of the plasma generation means to form the metalnitride as a film, for use as a barrier metal film, on a surface of thesubstrate;

[0101] oxygen gas supply means for supplying an oxygen gas into thechamber immediately before formation of the most superficial layer ofthe barrier metal film is completed; and

[0102] oxygen plasma generation means which converts the atmospherewithin the chamber into a plasma to generate an oxygen gas plasma sothat an oxide layer is formed on the most superficial layer of thebarrier metal film.

[0103] Thus, a barrier metal film comprising a metal nitride layer canbe prepared without the increase of the film thickness, and an oxidelayer gives satisfactory wettability by a metal deposited on the surfaceof the barrier metal film. Consequently, a barrier metal film productionapparatus can be achieved which is capable of forming a barrier metalfilm at a high speed with excellent burial properties in a very smallthickness, and also forming a barrier metal film with excellent adhesionto a metal formed as a film on the surface of the barrier metal film.

[0104] According to the present invention, there is also provided abarrier metal film production apparatus, comprising:

[0105] a chamber accommodating a substrate;

[0106] a metallic etched member provided in the chamber at a positionopposed to the substrate;

[0107] source gas supply means for supplying a source gas containing ahalogen into the chamber;

[0108] nitrogen-containing gas supply means for supplying a gascontaining nitrogen into the chamber;

[0109] plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas, andwhich converts the atmosphere within the chamber into a plasma togenerate a nitrogen-containing gas plasma so that a metal nitride isformed upon reaction between nitrogen and the precursor;

[0110] control means which makes a temperature of the substrate lowerthan a temperature of the plasma generation means to form the metalnitride as a film on a surface of the substrate, then makes thetemperature of the substrate lower than the temperature of the plasmageneration means and stops supply of the gas containing nitrogen fromthe nitrogen-containing gas supply means, thereby forming the metalcomponent of the precursor as a film on the metal nitride for use as abarrier metal film;

[0111] oxygen gas supply means for supplying an oxygen gas into thechamber immediately before formation of the most superficial layer ofthe barrier metal film is completed; and

[0112] oxygen plasma generation means which converts the atmospherewithin the chamber into a plasma to generate an oxygen gas plasma sothat an oxide layer is formed on the most superficial layer of thebarrier metal film.

[0113] Thus, a barrier metal film comprising a metal nitride layer and ametal layer can be prepared without the increase of the film thickness,and an oxide layer gives satisfactory wettability by a metal depositedon the surface of the barrier metal film. Consequently, a barrier metalfilm production apparatus can be achieved which is capable of forming abarrier metal film at a high speed with excellent burial properties, andalso forming a barrier metal film with excellent adhesion to a metalformed as a film on the surface of the barrier metal film.

[0114] According to the present invention, there is also provided abarrier metal film production apparatus, comprising:

[0115] a chamber accommodating a substrate;

[0116] a metallic etched member provided in the chamber at a positionopposed to the substrate;

[0117] source gas supply means for supplying a source gas containing ahalogen into the chamber;

[0118] plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas;

[0119] excitation means for exciting a gas containing nitrogen in amanner isolated from the chamber;

[0120] formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor;

[0121] control means which makes a temperature of the substrate lowerthan a temperature of the formation means to form the metal nitride as afilm on the substrate for use as a barrier metal film;

[0122] oxygen gas supply means for supplying an oxygen gas into thechamber immediately before formation of the most superficial layer ofthe barrier metal film is completed; and

[0123] oxygen plasma generation means which converts the atmospherewithin the chamber into a plasma to generate an oxygen gas plasma sothat an oxide layer is formed on the most superficial layer of thebarrier metal film.

[0124] Thus, a barrier metal film comprising a metal nitride layer canbe prepared without the increase of the film thickness, an oxide layergives satisfactory wettability by a metal deposited on the surface ofthe barrier metal film, and the substrate can be free from exposure to anitrogen-containing gas plasma. Consequently, a barrier metal filmproduction apparatus can be achieved which is capable of forming abarrier metal film at a high speed with excellent burial properties in avery small thickness without exerting the influence of thenitrogen-containing gas plasma upon the substrate, and also forming abarrier metal film with excellent adhesion to a metal formed as a filmon the surface of the barrier metal film.

[0125] According to the present invention, there is also provided abarrier metal film production apparatus, comprising:

[0126] a chamber accommodating a substrate;

[0127] a metallic etched member provided in the chamber at a positionopposed to the substrate;

[0128] source gas supply means for supplying a source gas containing ahalogen into the chamber;

[0129] plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas;

[0130] excitation means for exciting a gas containing nitrogen in amanner isolated from the chamber;

[0131] formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor;

[0132] control means which makes a temperature of the substrate lowerthan a temperature of the formation means to form the metal nitride as afilm on the substrate, and after film formation of the metal nitride,stops supply of the nitrogen-containing gas and makes the temperature ofthe substrate lower than a temperature of the etched member, therebyforming the metal component of the precursor as a film on the metalnitride on the substrate for use as a barrier metal film;

[0133] oxygen gas supply means for supplying an oxygen gas into thechamber immediately before formation of the most superficial layer ofthe barrier metal film is completed; and

[0134] oxygen plasma generation means which converts the atmospherewithin the chamber into a plasma to generate an oxygen gas plasma sothat an oxide layer is formed on the most superficial layer of thebarrier metal film.

[0135] Thus, a barrier metal film comprising a metal nitride layer canbe prepared without the increase of the film thickness, an oxide layergives satisfactory wettability by a metal deposited on the surface ofthe barrier metal film, and the substrate can be free from exposure to anitrogen-containing gas plasma. Consequently, a barrier metal filmproduction apparatus can be achieved which is capable of forming abarrier metal film at a high speed with excellent burial propertieswithout exerting the influence of the nitrogen-containing gas plasmaupon the substrate, and also forming a barrier metal film with excellentadhesion to a metal formed as a film on the surface of the barrier metalfilm.

[0136] The barrier metal film production apparatus may further comprisehydrogen gas supply means for supplying a hydrogen gas into the chamber;and hydroxyl group plasma generation means which converts the atmospherewithin the chamber into a plasma to generate a hydrogen gas plasma sothat hydroxyl groups are formed on the oxide layer.

[0137] Thus, hydroxyl groups are formed, so that hydrophilicity can beincreased, and adhesion of a metal deposited on the surface can befurther increased.

[0138] According to the present invention, there is also provided abarrier metal film production method comprising:

[0139] supplying a source gas containing a halogen and anitrogen-containing gas to an interior of a chamber between a substrateand a metallic etched member;

[0140] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and also convertingthe atmosphere within the chamber into a plasma to generate anitrogen-containing gas plasma so that a metal nitride is formed uponreaction between nitrogen and the precursor;

[0141] making a temperature of the substrate lower than a temperature ofplasma generation means to form the metal nitride as a barrier metalfilm on a surface of the substrate;

[0142] supplying a diluent gas to a site within the chamber above thesurface of the substrate; and

[0143] performing a surface treatment which converts the atmospherewithin the chamber into a plasma to generate a diluent gas plasma sothat nitrogen atoms in a superficial layer of the barrier metal film areremoved by the diluent gas plasma to decrease a nitrogen content of thesuperficial layer relative to an interior of a matrix of the barriermetal film.

[0144] Thus, a barrier metal film comprising a metal nitride layer and ametal layer can be prepared without the increase of the film thickness.Consequently, a barrier metal film production method can be achievedwhich is capable of forming a barrier metal film at a high speed withexcellent burial properties in a very small thickness, and also forminga barrier metal film with excellent adhesion to a metal formed as a filmon the surface of the barrier metal film.

[0145] The barrier metal film production method may further comprisesupplying an oxygen gas into the chamber immediately before formation ofthe most superficial layer of the barrier metal film is completed; andconverting the atmosphere within the chamber into a plasma to generatean oxygen gas plasma so that an oxide layer is formed on the mostsuperficial layer of the barrier metal film.

[0146] Thus, the oxide layer gives satisfactory wettability by a metaldeposited on the surface of the barrier metal film, thereby increasingadhesion to the metal.

[0147] According to the present invention, there is also provided abarrier metal film production method comprising:

[0148] supplying a source gas containing a halogen and anitrogen-containing gas to an interior of a chamber between a substrateand a metallic etched member;

[0149] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and also convertingthe atmosphere within the chamber into a plasma to generate anitrogen-containing gas plasma so that a metal nitride is formed uponreaction between nitrogen and the precursor;

[0150] making a temperature of the substrate lower than a temperature ofplasma generation means to form the metal nitride as a barrier metalfilm on a surface of the substrate;

[0151] supplying an oxygen gas to a site above the surface of thesubstrate; and

[0152] performing a surface treatment which converts the atmospherewithin the chamber into a plasma to generate an oxygen gas plasma sothat nitrogen atoms in a superficial layer of the barrier metal film areremoved by the oxygen gas plasma to decrease a nitrogen content of thesuperficial layer relative to an interior of a matrix of the barriermetal film, while forming an oxide layer on the most superficial layerof the barrier metal film.

[0153] Thus, a barrier metal film comprising a metal nitride layer and ametal layer can be prepared with a minimum nozzle construction withoutthe increase of the film thickness, and an oxide layer givessatisfactory wettability by a metal deposited on the surface of thebarrier metal film. Consequently, a barrier metal film production methodcan be achieved which is capable of forming a barrier metal film at ahigh speed with excellent burial properties in a very small thickness,and also forming a barrier metal film with excellent adhesion to a metalformed as a film on the surface of the barrier metal film.

[0154] According to the present invention, there is also provided abarrier metal film production method comprising:

[0155] supplying a source gas containing a halogen and anitrogen-containing gas to an interior of a chamber between a substrateand a metallic etched member;

[0156] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and also convertingthe atmosphere within the chamber into a plasma to generate anitrogen-containing gas plasma so that a metal nitride is formed uponreaction between nitrogen and the precursor;

[0157] making a temperature of the substrate lower than a temperature ofplasma generation means to form the metal nitride as a film on a surfaceof the substrate for use as a barrier metal film;

[0158] supplying an oxygen gas into the chamber immediately beforeformation of the most superficial layer of the barrier metal film iscompleted; and

[0159] converting the atmosphere within the chamber into a plasma togenerate an oxygen gas plasma so that an oxide layer is formed on themost superficial layer of the barrier metal film.

[0160] Thus, a barrier metal film comprising a metal nitride layer canbe prepared without the increase of the film thickness, and an oxidelayer gives satisfactory wettability by a metal deposited on the surfaceof the barrier metal film. Consequently, a barrier metal film productionmethod can be achieved which is capable of forming a barrier metal filmat a high speed with excellent burial properties in a very smallthickness, and also forming a barrier metal film with excellent adhesionto a metal formed as a film on the surface of the barrier metal film.

[0161] According to the present invention, there is also provided abarrier metal film production method comprising:

[0162] supplying a source gas containing a halogen and anitrogen-containing gas to an interior of a chamber between a substrateand a metallic etched member;

[0163] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and also convertingthe atmosphere within the chamber into a plasma to generate anitrogen-containing gas plasma so that a metal nitride is formed uponreaction between nitrogen and the precursor;

[0164] making a temperature of the substrate lower than a temperature ofplasma generation means to form the metal nitride as a film on a surfaceof the substrate, then making the temperature of the substrate lowerthan the temperature of the plasma generation means and stopping supplyof the gas containing nitrogen, thereby forming the metal component ofthe precursor as a film on the metal nitride for use as a barrier metalfilm;

[0165] supplying an oxygen gas into the chamber immediately beforeformation of the most superficial layer of the barrier metal film iscompleted; and

[0166] converting the atmosphere within the chamber into a plasma togenerate an oxygen gas plasma so that an oxide layer is formed on themost superficial layer of the barrier metal film.

[0167] Thus, a barrier metal film comprising a metal nitride layer and ametal layer can be prepared without the increase of the film thickness,and an oxide layer gives satisfactory wettability by a metal depositedon the surface of the barrier metal film. Consequently, a barrier metalfilm production method can be achieved which is capable of forming abarrier metal film at a high speed with excellent burial properties, andalso forming a barrier metal film with excellent adhesion to a metalformed as a film on the surface of the barrier metal film.

[0168] According to the present invention, there is also provided abarrier metal film production method comprising:

[0169] supplying a source gas containing a halogen and anitrogen-containing gas to an interior of a chamber between a substrateand a metallic etched member;

[0170] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and also exciting thegas containing nitrogen in a manner isolated from the chamberaccommodating the substrate;

[0171] forming a metal nitride upon reaction between excited nitrogenand the precursor;

[0172] making a temperature of the substrate lower than a temperature ofmeans for formation of the metal nitride to form the metal nitride as afilm on the substrate for use as a barrier metal film;

[0173] supplying an oxygen gas at a site above a surface of thesubstrate immediately before formation of the most superficial layer ofthe barrier metal film is completed; and

[0174] converting the atmosphere within the chamber into a plasma togenerate an oxygen gas plasma so that an oxide layer is formed on themost superficial layer of the barrier metal film.

[0175] Thus, a barrier metal film comprising a metal nitride layer canbe prepared without the increase of the film thickness, an oxide layergives satisfactory wettability by a metal deposited on the surface ofthe barrier metal film, and the substrate can be free from exposure to anitrogen-containing gas plasma. Consequently, a barrier metal filmproduction method can be achieved which is capable of forming a barriermetal film at a high speed with excellent burial properties in a verysmall thickness without exerting the influence of thenitrogen-containing gas plasma upon the substrate, and also forming abarrier metal film with excellent adhesion to a metal formed as a filmon the surface of the barrier metal film.

[0176] According to the present invention, there is also provided abarrier metal film production method comprising:

[0177] supplying a source gas containing a halogen and anitrogen-containing gas to an interior of a chamber between a substrateand a metallic etched member;

[0178] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and also exciting thegas containing nitrogen in a manner isolated from the chamberaccommodating the substrate;

[0179] forming a metal nitride upon reaction between excited nitrogenand the precursor;

[0180] making a temperature of the substrate lower than a temperature ofmeans for formation of the metal nitride to form the metal nitride as afilm on the substrate, and after film formation of the metal nitride,stopping supply of the nitrogen-containing gas and making thetemperature of the substrate lower than a temperature of the etchedmember, thereby forming the metal component of the precursor as a filmon the metal nitride on the substrate for use as a barrier metal film;

[0181] supplying an oxygen gas at a site above a surface of thesubstrate immediately before formation of the most superficial layer ofthe barrier metal film is completed; and

[0182] converting the atmosphere within the chamber into a plasma togenerate an oxygen gas plasma so that an oxide layer is formed on themost superficial layer of the barrier metal film.

[0183] Thus, a barrier metal film comprising a metal nitride layer canbe prepared without the increase of the film thickness, an oxide layergives satisfactory wettability by a metal deposited on the surface ofthe barrier metal film, and the substrate can be free from exposure to anitrogen-containing gas plasma. Consequently, a barrier metal filmproduction method can be achieved which is capable of forming a barriermetal film at a high speed with excellent burial properties withoutexerting the influence of the nitrogen-containing gas plasma upon thesubstrate, and also forming a barrier metal film with excellent adhesionto a metal formed as a film on the surface of the barrier metal film.

[0184] The barrier metal film production method may further comprisesupplying a hydrogen gas into the chamber; and converting the atmospherewithin the chamber into a plasma to generate a hydrogen gas plasma sothat hydroxyl groups are formed on the oxide layer.

[0185] Thus, hydrophilicity can be increased, so that adhesion of ametal deposited on the surface can be further increased.

[0186] According to the present invention, there is also provided abarrier metal film production method involving treatment of a surface ofa substrate having a barrier metal film of a metal nitride formedthereon, comprising:

[0187] performing a surface treatment which removes nitrogen atoms in asuperficial layer of the barrier metal film to decrease a nitrogencontent of the superficial layer relative to an interior of a matrix ofthe barrier metal film, thereby substantially forming a metal layer onthe superficial layer.

[0188] Thus, the substantial metal layer and the metal nitride layer canbe formed with a single-layer thickness, and a barrier metal film with avery small thickness can be produced, with diffusion of metal beingprevented and adhesion to the metal being retained. Consequently, ametal wiring process can be stabilized.

[0189] According to the present invention, there is also provided ametal film comprising a metal layer substantially formed on asuperficial layer of a barrier metal film of a metal nitride formed on asurface of a substrate, said metal layer being formed by performing asurface treatment which removes nitrogen atoms in the superficial layerof the barrier metal film to decrease a nitrogen content of thesuperficial layer relative to an interior of a matrix of the barriermetal film.

[0190] Thus, there is obtained a metal film which has a barrier metalfilm comprising the substantial metal layer and the metal nitride layerformed with a single-layer thickness, and produced with a very smallthickness, with diffusion of metal being prevented and adhesion to themetal being retained, and which can stabilize a metal wiring process.

[0191] According to the present invention, there is also provided abarrier metal film production method involving treatment of a surface ofa substrate having a barrier metal film of a metal nitride formedthereon, comprising:

[0192] performing a surface treatment which etches the barrier metalfilm on the surface of the substrate with a diluent gas plasma toflatten the barrier metal film.

[0193] Thus, a barrier metal film can be produced, with diffusion ofmetal being prevented and adhesion to the metal being retained.Consequently, a metal wiring process can be stabilized.

[0194] According to the present invention, there is also provided abarrier metal film production method involving treatment of a surface ofa substrate having a barrier metal film of a metal nitride formedthereon, comprising:

[0195] performing a surface treatment which etches the barrier metalfilm on the surface of the substrate with a diluent gas plasma toflatten the barrier metal film, and removes nitrogen atoms in asuperficial layer of the barrier metal film by the diluent gas plasma todecrease a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film.

[0196] Thus, the substantial metal layer and the metal nitride layer canbe formed with a single-layer thickness, and a barrier metal film with avery small thickness can be produced, with diffusion of metal beingprevented and adhesion to the metal being retained. Consequently, ametal wiring process can be stabilized.

[0197] According to the present invention, there is also provided ametal film production method comprising:

[0198] supplying a source gas containing a halogen to an interior of achamber between a substrate and a metallic etched member;

[0199] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and also exciting agas containing nitrogen in a manner isolated from the chamberaccommodating the substrate;

[0200] forming a metal nitride upon reaction between excited nitrogenand the precursor;

[0201] making a temperature of the substrate lower than a temperature ofmeans for formation of the metal nitride to form the metal nitride as afilm on the substrate for use as a barrier metal film; and

[0202] performing a surface treatment which etches the barrier metalfilm on a surface of the substrate with a diluent gas plasma to flattenthe barrier metal film.

[0203] Thus, a barrier metal film can be produced such that the barriermetal film is prepared, and then subjected to a treatment for preventingdiffusion of metal and retaining adhesion to the metal. Consequently, ametal wiring process can be stabilized.

[0204] According to the present invention, there is also provided ametal film production method comprising:

[0205] supplying a source gas containing a halogen to an interior of achamber between a substrate and a metallic etched member;

[0206] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and also exciting agas containing nitrogen in a manner isolated from the chamberaccommodating the substrate;

[0207] forming a metal nitride upon reaction between excited nitrogenand the precursor;

[0208] making a temperature of the substrate lower than a temperature ofmeans for formation of the metal nitride to form the metal nitride as afilm on the substrate for use as a barrier metal film; and

[0209] performing a surface treatment which etches the barrier metalfilm on a surface of the substrate with a diluent gas plasma to flattenthe barrier metal film, and removes nitrogen atoms in a superficiallayer of the barrier metal film by the diluent gas plasma to decrease anitrogen content of the superficial layer relative to an interior of amatrix of the barrier metal film.

[0210] Thus, after a barrier metal film is prepared, the substantialmetal layer and the metal nitride layer can be formed with asingle-layer thickness. Hence, a barrier metal film having a very smallthickness can be produced, with diffusion of metal being prevented andadhesion to the metal being retained. Consequently, a metal wiringprocess can be stabilized.

[0211] According to the present invention, there is also provided ametal film production method comprising:

[0212] performing a surface treatment which generates a diluent gasplasma within a chamber accommodating a substrate having a barrier metalfilm of a metal nitride formed thereon, to etch the barrier metal filmon a surface of the substrate with the diluent gas plasma, therebyflattening the barrier metal film;

[0213] then supplying a source gas containing a halogen into thechamber;

[0214] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that an etched member made of a metal isetched with the source gas plasma to form a precursor within the chamberfrom a metal component contained in the etched member and the sourcegas; and

[0215] making a temperature of the substrate lower than a temperature ofthe etched member to form the metal component of the precursor as a filmon the substrate having the barrier metal film flattened.

[0216] Thus, a metal can be formed as a film through the production of abarrier metal film subjected to a treatment for preventing diffusion ofmetal and retaining adhesion to the metal. Consequently, a metal wiringprocess can be stabilized.

[0217] According to the present invention, there is also provided ametal film production method comprising:

[0218] performing a surface treatment which generates a diluent gasplasma within a chamber accommodating a substrate having a barrier metalfilm of a metal nitride formed thereon, to etch the barrier metal filmon a surface of the substrate with the diluent gas plasma, therebyflattening the barrier metal film, and removes nitrogen atoms in asuperficial layer of the barrier metal film by the diluent gas plasma todecrease a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film;

[0219] then supplying a source gas containing a halogen into thechamber;

[0220] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that an etched member made of a metal isetched with the source gas plasma to form a precursor within the chamberfrom a metal component contained in the etched member and the sourcegas; and

[0221] making a temperature of the substrate lower than a temperature ofthe etched member to form the metal component of the precursor as a filmon the substrate having the barrier metal film flattened and having thenitrogen content of the superficial layer relatively decreased.

[0222] Thus, the substantial metal layer and the metal nitride layer canbe formed with a single-layer thickness. Hence, a metal can be formed asa film through the production of a barrier metal film having a verysmall thickness while preventing diffusion of metal and retainingadhesion to the metal. Consequently, a metal wiring process can bestabilized.

[0223] The metal film production method may further comprise applying adensification treatment for densifying metal atoms in a superficiallayer of the barrier metal film after flattening the barrier metal filmand also relatively decreasing the nitrogen content of the superficiallayer.

[0224] Thus, diffusion of the component of the metal film can beprevented reliably.

[0225] In the metal film production method, the diluent gas plasma maybe an argon gas plasma. Thus, the treatment can be performed reliablywith the use of an inexpensive gas.

[0226] According to the present invention, there is also provided ametal film production apparatus, comprising:

[0227] a chamber accommodating a substrate;

[0228] a metallic etched member provided in the chamber at a positionopposed to the substrate;

[0229] halogen gas supply means for supplying a source gas containing ahalogen to an interior of the chamber between the substrate and theetched member;

[0230] barrier plasma generation means which converts an atmospherewithin the chamber into a plasma to generate a source gas plasma so thatthe etched member is etched with the source gas plasma to form aprecursor from a metal component contained in the etched member and thesource gas;

[0231] excitation means for exciting a gas containing nitrogen in amanner isolated from the chamber;

[0232] formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor;

[0233] control means which makes a temperature of the substrate lowerthan a temperature of the formation means to form the metal nitride as afilm on the substrate for use as a barrier metal film;

[0234] diluent gas supply means for supplying a diluent gas to a siteabove a surface of the substrate; and

[0235] surface treatment plasma generation means which converts theatmosphere within the chamber into a plasma to generate a diluent gasplasma so that the barrier metal film on the surface of the substrate isetched with the diluent gas plasma to flatten the barrier metal film.

[0236] Thus, there can be produced a barrier metal film subjected totreatment for preventing diffusion of metal and retaining adhesion tothe metal. Consequently, a metal wiring process can be stabilized.

[0237] According to the present invention, there is also provided ametal film production apparatus, comprising:

[0238] a chamber accommodating a substrate;

[0239] a metallic etched member provided in the chamber at a positionopposed to the substrate;

[0240] halogen gas supply means for supplying a source gas containing ahalogen to an interior of the chamber between the substrate and theetched member;

[0241] barrier plasma generation means which converts an atmospherewithin the chamber into a plasma to generate a source gas plasma so thatthe etched member is etched with the source gas plasma to form aprecursor from a metal component contained in the etched member and thesource gas;

[0242] excitation means for exciting a gas containing nitrogen in amanner isolated from the chamber;

[0243] formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor;

[0244] control means which makes a temperature of the substrate lowerthan a temperature of the formation means to form the metal nitride as afilm on the substrate for use as a barrier metal film;

[0245] diluent gas supply means for supplying a diluent gas to a siteabove a surface of the substrate; and

[0246] surface treatment plasma generation means for performing asurface treatment which converts the atmosphere within the chamber intoa plasma to generate a diluent gas plasma so that the barrier metal filmon the surface of the substrate is etched with the diluent gas plasma toflatten the barrier metal film, and removes nitrogen atoms in asuperficial layer of the barrier metal film to decrease a nitrogencontent of the superficial layer relative to an interior of a matrix ofthe barrier metal film.

[0247] Thus, the substantial metal layer and the metal nitride layer canbe formed with a single-layer thickness. Hence, a barrier metal filmhaving a very small thickness can be produced, with diffusion of metalbeing prevented and adhesion to the metal being retained. Consequently,a metal wiring process can be stabilized.

[0248] According to the present invention, there is also provided ametal film production apparatus, comprising:

[0249] a chamber accommodating a substrate having a barrier metal filmof a metal nitride formed thereon;

[0250] diluent gas supply means for supplying a diluent gas to aninterior of the chamber above a surface of the substrate;

[0251] surface treatment plasma generation means which converts anatmosphere within the chamber into a plasma to generate a diluent gasplasma so that the barrier metal film on the surface of the substrate isetched with the diluent gas plasma to flatten the barrier metal film;

[0252] a metallic etched member provided in the chamber;

[0253] source gas supply means for supplying a source gas containing ahalogen to an interior of the chamber between the substrate and theetched member;

[0254] plasma generation means which converts the source gas containingthe halogen into a plasma to generate a source gas plasma so that theetched member is etched with the source gas plasma to form a precursorfrom a metal component contained in the etched member and the sourcegas; and

[0255] control means which makes a temperature of the substrate lowerthan a temperature of the etched member to form the metal component ofthe precursor as a film on the flattened barrier metal film.

[0256] Thus, a metal film can be formed through the production of abarrier metal film subjected to a treatment for preventing diffusion ofmetal and retaining adhesion to the metal. Consequently, a metal wiringprocess can be stabilized.

[0257] According to the present invention, there is also provided ametal film production apparatus, comprising:

[0258] a chamber accommodating a substrate having a barrier metal filmof a metal nitride formed thereon;

[0259] diluent gas supply means for supplying a diluent gas to aninterior of the chamber above a surface of the substrate;

[0260] surface treatment plasma generation means which converts anatmosphere within the chamber into a plasma to generate a diluent gasplasma so that the barrier metal film on the surface of the substrate isetched with the diluent gas plasma to flatten the barrier metal film,and also removes nitrogen atoms in a superficial layer of the barriermetal film by the diluent gas plasma to decrease a nitrogen content ofthe superficial layer relative to an interior of a matrix of the barriermetal film;

[0261] a metallic etched member provided in the chamber;

[0262] source gas supply means for supplying a source gas containing ahalogen to an interior of the chamber between the substrate and theetched member;

[0263] plasma generation means which converts the source gas containingthe halogen into a plasma to generate a source gas plasma so that theetched member is etched with the source gas plasma to form a precursorfrom a metal component contained in the etched member and the sourcegas; and

[0264] control means which makes a temperature of the substrate lowerthan a temperature of the etched member to form the metal component ofthe precursor as a film on the barrier metal film flattened and havingthe nitrogen content of the superficial layer relatively decreased.

[0265] Thus, the substantial metal layer and the metal nitride layer canbe formed with a single-layer thickness. Hence, a metal film can beformed through the production of a barrier metal film having a verysmall thickness while preventing diffusion of metal and retainingadhesion to the metal. Consequently, a metal wiring process can bestabilized.

[0266] The metal film production apparatus may further comprisedensification treatment means for densifying metal atoms in thesuperficial layer after flattening the barrier metal film and alsorelatively decreasing the nitrogen content of the superficial layer.Thus, diffusion of the component of the metal film can be preventedreliably.

[0267] In the metal film production apparatus, the diluent gas plasmamay be an argon gas plasma. Thus, the treatment can be performedreliably with the use of an inexpensive gas.

[0268] According to the present invention, there is also provided ametal film formed by flattening a barrier metal film of a metal nitrideon a surface of a substrate by etching with a diluent gas plasma.

[0269] Thus, the resulting metal film has a barrier metal film retainingadhesion, and can stabilize a metal wiring process.

[0270] According to the present invention, there is also provided ametal film formed by a surface treatment which flattens a barrier metalfilm of a metal nitride on a surface of a substrate by etching with adiluent gas plasma, and removes nitrogen atoms in a superficial layer ofthe barrier metal film by the diluent gas plasma to decrease a nitrogencontent of the superficial layer relative to an interior of a matrix ofthe barrier metal film.

[0271] Thus, there is obtained a metal film which has a barrier metalfilm comprising the substantial metal layer and the metal nitride layerformed with a single-layer thickness, and produced with a very smallthickness, with diffusion of metal being prevented and adhesion to themetal being retained, and which can stabilize a metal wiring process.

[0272] According to the present invention, there is also provided ametal film production method involving treatment of a surface of asubstrate having a barrier metal film of a metal nitride formed thereon,comprising:

[0273] performing a surface treatment which reacts the barrier metalfilm on the surface of the substrate in a reducing gas atmosphere toremove nitrogen atoms in a superficial layer of the barrier metal film,thereby decreasing a nitrogen content of the superficial layer relativeto an interior of a matrix of the barrier metal film.

[0274] Thus, a barrier metal film with a very small thickness andcomprising the substantial metal layer and the metal nitride layerformed with a single-layer thickness can be produced, with diffusion ofmetal being prevented and adhesion to the metal being retained.Consequently, a metal wiring process can be stabilized.

[0275] According to the present invention, there is also provided ametal film production method comprising:

[0276] supplying a source gas containing a halogen to an interior of achamber between a substrate and a metallic etched member;

[0277] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and also exciting agas containing nitrogen in a manner isolated from the chamberaccommodating the substrate;

[0278] forming a metal nitride upon reaction between excited nitrogenand the precursor;

[0279] making a temperature of the substrate lower than a temperature ofmeans for formation of the metal nitride to form the metal nitride as afilm on the substrate for use as a barrier metal film; and

[0280] performing a surface treatment which reacts the barrier metalfilm on a surface of the substrate in a reducing gas atmosphere toremove nitrogen atoms in a superficial layer of the barrier metal film,thereby decreasing a nitrogen content of the superficial layer relativeto an interior of a matrix of the barrier metal film.

[0281] Thus, a barrier metal film with a very small thickness andcomprising the substantial metal layer and the metal nitride layerformed with a single-layer thickness can be produced, with diffusion ofmetal being prevented and adhesion to the metal being retained.Consequently, a metal wiring process can be stabilized.

[0282] According to the present invention, there is also provided ametal film production method comprising:

[0283] performing a surface treatment in a chamber accommodating asubstrate having a barrier metal film of a metal nitride formed thereon,said surface treatment comprising reacting the barrier metal film on asurface of the substrate in a reducing gas atmosphere to remove nitrogenatoms in a superficial layer of the barrier metal film, therebydecreasing a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film;

[0284] then supplying a source gas containing a halogen into thechamber;

[0285] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that a metallic etched member is etchedwith the source gas plasma to form a precursor within the chamber from ametal component contained in the etched member and the source gas; and

[0286] making a temperature of the substrate lower than a temperature ofthe etched member to form the metal component of the precursor as a filmon the substrate having the barrier metal film flattened thereon.

[0287] Thus, a metal film can be formed through the production of abarrier metal film having a very small thickness and comprising thesubstantial metal layer and the metal nitride layer formed with asingle-layer thickness, while preventing diffusion of metal andretaining adhesion to the metal. Consequently, a metal wiring processcan be stabilized.

[0288] According to the present invention, there is also provided ametal film production apparatus, comprising:

[0289] a chamber accommodating a substrate;

[0290] a metallic etched member provided in the chamber at a positionopposed to the substrate;

[0291] halogen gas supply means for supplying a source gas containing ahalogen to an interior of the chamber between the substrate and theetched member;

[0292] barrier plasma generation means which converts an atmospherewithin the chamber into a plasma to generate a source gas plasma so thatthe etched member is etched with the source gas plasma to form aprecursor from a metal component contained in the etched member and thesource gas;

[0293] excitation means for exciting a gas containing nitrogen in amanner isolated from the chamber;

[0294] formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor;

[0295] control means which makes a temperature of the substrate lowerthan a temperature of the formation means to form the metal nitride as afilm on the substrate for use as a barrier metal film;

[0296] reducing gas supply means for supplying a reducing gas to a siteabove a surface of the substrate; and

[0297] surface treatment means which reacts the barrier metal film onthe surface of the substrate in a reducing gas atmosphere to removenitrogen atoms in a superficial layer of the barrier metal film, therebydecreasing a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film.

[0298] Thus, a barrier metal film with a very small thickness andcomprising the substantial metal layer and the metal nitride layerformed with a single-layer thickness can be produced, with diffusion ofmetal being prevented and adhesion to the metal being retained.Consequently, a metal wiring process can be stabilized.

[0299] According to the present invention, there is also provided ametal film production apparatus, comprising:

[0300] a chamber accommodating a substrate having a barrier metal filmof a metal nitride formed thereon;

[0301] reducing gas supply means for supplying a reducing gas to a siteabove a surface of the substrate;

[0302] surface treatment means which reacts the barrier metal film onthe surface of the substrate in a reducing gas atmosphere to removenitrogen atoms in a superficial layer of the barrier metal film, therebydecreasing a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film;

[0303] a metallic etched member provided in the chamber;

[0304] source gas supply means for supplying a source gas containing ahalogen to an interior of the chamber between the substrate and theetched member;

[0305] plasma generation means which converts the source gas containingthe halogen into a plasma to generate a source gas plasma so that theetched member is etched with the source gas plasma to form a precursorfrom a metal component contained in the etched member and the sourcegas; and

[0306] control means which makes a temperature of the substrate lowerthan a temperature of the etched member to form the metal component ofthe precursor as a film on the barrier metal film having the nitrogencontent of the superficial layer relatively decreased.

[0307] Thus, a metal film can be formed through the production of abarrier metal film having a very small thickness and comprising thesubstantial metal layer and the metal nitride layer formed with asingle-layer thickness, while preventing diffusion of metal andretaining adhesion to the metal. Consequently, a metal wiring processcan be stabilized.

[0308] According to the present invention, there is also provided ametal film formed by a surface treatment which reacts a barrier metalfilm of a metal nitride on a surface of a substrate in a reducing gasatmosphere to remove nitrogen atoms in a superficial layer of thebarrier metal film, thereby decreasing a nitrogen content of thesuperficial layer relative to an interior of a matrix of the barriermetal film.

[0309] Thus, there is obtained a metal film which has a barrier metalfilm comprising the substantial metal layer and the metal nitride layerformed with a single-layer thickness, and produced with a very smallthickness, with diffusion of metal being prevented and adhesion to themetal being retained, and which can stabilize a metal wiring process.

[0310] According to the present invention, there is also provided ametal film production method involving treatment of a surface of asubstrate having a barrier metal film of a metal nitride formed thereon,comprising:

[0311] performing a surface treatment which forms nuclei of siliconatoms on a surface of the barrier metal film on the surface of thesubstrate by a gas plasma containing silicon.

[0312] Thus, a barrier metal film with a very small thickness can beproduced, with adhesion to metal being retained. Consequently, a metalwiring process can be stabilized.

[0313] According to the present invention, there is also provided ametal film production method comprising:

[0314] supplying a source gas containing a halogen to an interior of achamber between a substrate and a metallic etched member;

[0315] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and also exciting agas containing nitrogen in a manner isolated from the chamberaccommodating the substrate;

[0316] forming a metal nitride upon reaction between excited nitrogenand the precursor;

[0317] making a temperature of the substrate lower than a temperature ofmeans for formation of the metal nitride to form the metal nitride as afilm on the substrate for use as a barrier metal film; and

[0318] performing a surface treatment which forms nuclei of siliconatoms on a surface of the barrier metal film on a surface of thesubstrate by a gas plasma containing silicon.

[0319] Thus, a barrier metal film with a very small thickness can beproduced, with adhesion to metal being retained. Consequently, a metalwiring process can be stabilized.

[0320] According to the present invention, there is also provided ametal film production method comprising:

[0321] performing a surface treatment in a chamber accommodating asubstrate having a barrier metal film of a metal nitride formed thereon,said surface treatment comprising forming nuclei of silicon atoms on asurface of the barrier metal film on a surface of the substrate by a gasplasma containing silicon;

[0322] then supplying a source gas containing a halogen into thechamber;

[0323] converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that a metallic etched member is etchedwith the source gas plasma to form a precursor within the chamber from ametal component contained in the etched member and the source gas; and

[0324] making a temperature of the substrate lower than a temperature ofthe etched member to form the metal component of the precursor as a filmon the substrate having the nuclei of silicon atoms formed on thesurface of the barrier metal film.

[0325] Thus, a metal film can be formed through the production of abarrier metal film having a very small thickness and retaining adhesionto metal. Consequently, a metal wiring process can be stabilized.

[0326] According to the present invention, there is also provided ametal film production apparatus, comprising:

[0327] a chamber accommodating a substrate;

[0328] a metallic etched member provided in the chamber at a positionopposed to the substrate;

[0329] halogen gas supply means for supplying a source gas containing ahalogen to an interior of the chamber between the substrate and theetched member;

[0330] barrier plasma generation means which converts an atmospherewithin the chamber into a plasma to generate a source gas plasma so thatthe etched member is etched with the source gas plasma to form aprecursor from a metal component contained in the etched member and thesource gas;

[0331] excitation means for exciting a gas containing nitrogen in amanner isolated from the chamber;

[0332] formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor;

[0333] control means which makes a temperature of the substrate lowerthan a temperature of the formation means to form the metal nitride as afilm on the substrate for use as a barrier metal film;

[0334] silicon-containing gas supply means for supplying a gascontaining silicon to a site above a surface of the substrate; and

[0335] surface treatment plasma generation means which generates a gasplasma containing silicon to form nuclei of silicon atoms on a surfaceof the barrier metal film on the surface of the substrate.

[0336] Thus, a barrier metal film with a very small thickness can beproduced, with adhesion to metal being retained. Consequently, a metalwiring process can be stabilized.

[0337] According to the present invention, there is also provided ametal film production apparatus, comprising:

[0338] a chamber accommodating a substrate having a barrier metal filmof a metal nitride formed thereon;

[0339] silicon-containing gas supply means for supplying a gascontaining silicon to a site above a surface of the substrate;

[0340] surface treatment plasma generation means which generates a gasplasma containing silicon to form nuclei of silicon atoms on a surfaceof the barrier metal film on the surface of the substrate;

[0341] a metallic etched member provided in the chamber;

[0342] source gas supply means for supplying a source gas containing ahalogen to an interior of the chamber between the substrate and theetched member;

[0343] plasma generation means which converts the source gas containingthe halogen into a plasma to generate a source gas plasma so that theetched member is etched with the source gas plasma to form a precursorfrom a metal component contained in the etched member and the sourcegas; and

[0344] control means which makes a temperature of the substrate lowerthan a temperature of the etched member to form the metal component ofthe precursor as a film on the barrier metal film having the nuclei ofsilicon atoms formed on the surface thereof.

[0345] Thus, a metal film can be formed through the production of abarrier metal film having a very small thickness and retaining adhesionto metal. Consequently, a metal wiring process can be stabilized.

[0346] According to the present invention, there is also provided ametal film formed by applying a surface treatment to a barrier metalfilm of a metal nitride on a surface of a substrate such that nuclei ofsilicon atoms are formed on a surface of the barrier metal film on thesurface of the substrate by a gas plasma containing silicon.

[0347] Thus, there is obtained a metal film which has a barrier metalfilm having a very small thickness and retaining adhesion to metal, andwhich can stabilize a metal wiring process.

BRIEF DESCRIPTION OF THE DRAWINGS

[0348] The present invention will become more fully understood from thedetailed description given hereinbelow and the accompanying drawingswhich are given by way of illustration only, and thus are not limitativeof the present invention, and wherein:

[0349]FIG. 1 is a schematic side view of a barrier metal film productionapparatus according to a first embodiment of the present invention;

[0350]FIG. 2 is a detail view of a substrate on which a barrier metalfilm has been produced;

[0351]FIG. 3 is a schematic side view of a barrier metal film productionapparatus according to a second embodiment of the present invention;

[0352]FIG. 4 is a view taken along the arrowed line IV-IV of FIG. 3;

[0353]FIG. 5 is a view taken along the arrowed line V-V of FIG. 4;

[0354]FIG. 6 is a schematic side view of a barrier metal film productionapparatus according to a third embodiment of the present invention;

[0355]FIG. 7 is a schematic side view of a barrier metal film productionapparatus according to a fourth embodiment of the present invention;

[0356]FIG. 8 is a schematic side view of a barrier metal film productionapparatus according to a fifth embodiment of the present invention;

[0357]FIG. 9 is a schematic side view of a barrier metal film productionapparatus according to a sixth embodiment of the present invention;

[0358]FIG. 10 is a schematic side view of a barrier metal filmproduction apparatus according to a seventh embodiment of the presentinvention;

[0359]FIG. 11 is a schematic side view of a barrier metal filmproduction apparatus according to an eighth embodiment of the presentinvention;

[0360]FIG. 12 is a schematic side view of a barrier metal filmproduction apparatus according to a ninth embodiment of the presentinvention;

[0361]FIG. 13 is a sectional view of a substrate illustrating a barriermetal film;

[0362]FIG. 14 is a concept view of a barrier metal film in a treatmentfor denitrification;

[0363]FIG. 15 is a concept view of the barrier metal film in thetreatment for denitrification;

[0364]FIG. 16 is a concept view of a barrier metal film in a treatmentfor oxide layer formation;

[0365]FIG. 17 is a graph representing the relationship between thecontact angle of copper particles and the oxygen concentration of thesubstrate;

[0366]FIG. 18 is a concept view of a barrier metal film in a treatmentfor hydroxyl group formation;

[0367]FIG. 19 is a schematic construction drawing showing anotherexample of diluent gas supply means;

[0368]FIG. 20 is a schematic construction drawing of a barrier metalfilm production apparatus according to a tenth embodiment of the presentinvention;

[0369]FIG. 21 is a concept view of an example of production of a barriermetal film by the barrier metal film production apparatus according tothe tenth embodiment of the present invention;

[0370]FIG. 22 is a schematic side view of a barrier metal filmproduction apparatus according to an eleventh embodiment of the presentinvention;

[0371]FIG. 23 is a schematic side view of a barrier metal filmproduction apparatus according to a twelfth embodiment of the presentinvention;

[0372]FIG. 24 is a view taken along the arrowed line XIII-XIII of FIG.23;

[0373]FIG. 25 is a view taken along the arrowed line XIV-XIV of FIG. 24;

[0374]FIG. 26 is a schematic side view of a barrier metal filmproduction apparatus according to a thirteenth embodiment of the presentinvention;

[0375]FIG. 27 is a schematic side view of a barrier metal filmproduction apparatus according to a fourteenth embodiment of the presentinvention;

[0376]FIG. 28 is an outline drawing of an apparatus for a film formationprocess;

[0377]FIG. 29 is a schematic side view of a metal film productionapparatus according to a fifteenth embodiment of the present invention;

[0378]FIG. 30 is a schematic construction drawing showing anotherexample of diluent gas supply means;

[0379]FIG. 31 is a sectional view of a substrate illustrating a barriermetal film;

[0380]FIG. 32 is a concept view of a barrier metal film in a treatmentfor denitrification;

[0381]FIG. 33 is a concept view of the barrier metal film in thetreatment for denitrification;

[0382]FIG. 34 is a schematic side view of a metal film productionapparatus according to a sixteenth embodiment of the present invention;

[0383]FIG. 35 is a view taken along the arrowed line VIII-VIII of FIG.34;

[0384]FIG. 36 is a view taken along the arrowed line IX-IX of FIG. 35;

[0385]FIG. 37 is a schematic side view of a metal film productionapparatus according to a seventeenth embodiment of the presentinvention;

[0386]FIG. 38 is a schematic side view of a metal film productionapparatus according to an eighteenth embodiment of the presentinvention;

[0387]FIG. 39 is a schematic side view of a metal film productionapparatus according to a nineteenth embodiment of the present invention;

[0388]FIG. 40 is a conceptual construction drawing of a metal filmproduction apparatus according to a twentieth embodiment of the presentinvention;

[0389]FIG. 41 is a concept view of a barrier metal film in a treatmentfor denitrification;

[0390]FIG. 42 is a schematic construction drawing of a metal filmproduction apparatus according to a twenty-first embodiment of thepresent invention; and

[0391]FIG. 43 is a concept view of a barrier metal film in formation ofnuclei of Si.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0392] The first embodiment of the barrier metal film productionapparatus and barrier metal film production method of the presentinvention will be described with reference to FIGS. 1 and 2. FIG. 1 is aschematic side view of the barrier metal film production apparatusaccording to the first embodiment of the present invention. FIG. 2 showsdetails of a substrate on which a barrier metal film has been prepared.

[0393] As shown in the drawings, a support platform 2 is provided nearthe bottom of a cylindrical chamber 1 made of, say, a ceramic (aninsulating material), and a substrate 3 is placed on the supportplatform 2. Temperature control means 6 equipped with a heater 4 andrefrigerant flow-through means 5 is provided in the support platform 2so that the support platform 2 is controlled to a predeterminedtemperature (for example, a temperature at which the substrate 3 ismaintained at 100 to 200° C.) by the temperature control means 6.

[0394] An upper surface of the chamber 1 is an opening, which is closedwith a metal member 7, as an etched member, made of a metal (e.g., W,Ti, Ta, or TiSi). The interior of the chamber 1 closed with the metalmember 7 is maintained at a predetermined pressure by a vacuum device 8.A plasma antenna 9, as a coiled winding antenna 9 of plasma generationmeans, is provided around a cylindrical portion of the chamber 1. Amatching instrument 10 and a power source 11 are connected to the plasmaantenna 9 to supply power.

[0395] Nozzles 12 for supplying a source gas (a Cl₂ gas diluted with Heor Ar to a chlorine concentration of ≦50%, preferably about 10%),containing chlorine as a halogen, to the interior of the chamber 1 areconnected to the cylindrical portion of the chamber 1 below the metalmember 7. The nozzle 12 is open toward the horizontal, and is fed withthe source gas via a flow controller 13. Fluorine (F), bromine (Br) oriodine (I) can also be applied as the halogen to be incorporated intothe source gas.

[0396] Slit-shaped opening portions 14 are formed at a plurality oflocations (for example, four locations) in the periphery of a lower partof the cylindrical portion of the chamber 1, and one end of a tubularpassage 15 is fixed to each of the opening portions 14. A tubularexcitation chamber 16 made of an insulator is provided halfway throughthe passage 15, and a coiled plasma antenna 17 is provided around theexcitation chamber 16. The plasma antenna 17 is connected to a matchinginstrument 18 and a power source 19 to receive power. The plasma antenna17, the matching instrument 18 and the power source 19 constituteexcitation means. A flow controller 20 is connected to the other end ofthe passage 15, and an ammonia gas (NH₃ gas) as a nitrogen-containinggas is supplied into the passage 15 via the flow controller 20.

[0397] With the above-described barrier metal film production apparatus,the source gas is supplied through the nozzles 12 to the interior of thechamber 1, and electromagnetic waves are shot from the plasma antenna 9into the chamber 1. As a result, the Cl₂ gas is ionized to generate aCl₂ gas plasma (source gas plasma) 21. The Cl₂ gas plasma 21 causes anetching reaction to the metal member 7, forming a precursor(M_(x)Cl_(y): M is a metal such as W, Ti, Ta or TiSi) 22.

[0398] Separately, the NH₃ gas is supplied into the passage 15 via theflow controller 20 and fed into the excitation chamber 16. By shootingelectromagnetic waves from the plasma antenna 17 into the excitationchamber 16, the NH₃ gas is ionized to generate an NH₃ gas plasma 23.Since a predetermined differential pressure has been established betweenthe pressure inside the chamber 1 and the pressure inside the excitationchamber 16 by the vacuum device 8, the excited ammonia of the NH₃ gasplasma 23 in the excitation chamber 16 is fed to the precursor(M_(x)Cl_(y)) 22 inside the chamber 1 through the opening portion 14.

[0399] That is, excitation means for exciting the nitrogen-containinggas in the excitation chamber 16 isolated from the chamber 1 isconstructed. Because of this construction, the metal component of theprecursor (M_(x)Cl_(y)) 22 and ammonia react to form a metal nitride(MN) (i.e., formation means). At this time, the metal member 7 and theexcitation chamber 16 are maintained by the plasmas at predeterminedtemperatures (e.g., 200 to 400° C.) which are higher than thetemperature of the substrate 3.

[0400] The metal nitride (MN) formed within the chamber 1 is transportedtoward the substrate 3 controlled to a low temperature, whereby a thinMN film 24 is formed on the surface of the substrate 3. After the thinMN film 24 is formed, the supply of the NH₃ gas and the supply of powerto the power source 19 are cut off. Thus, the precursor (M_(x)Cl_(y)) 22is transported toward the substrate 3 controlled to a lower temperaturethan the temperature of the metal member 7. The precursor (M_(x)Cl_(y))22 transported toward the substrate 3 is converted into only metal (M)ions by a reduction reaction, and directed at the substrate 3 to form athin M film 25 on the thin MN film 24 on the substrate 3. A barriermetal film 26 is composed of the thin MN film 24 and the thin M film 25(see FIG. 2).

[0401] The reaction for formation of the thin MN film 24 can beexpressed by:

2MCl+2NH₃→2MN↓+HCl↑+2H₂↑

[0402] The reaction for formation of the thin M film 25 can be expressedby:

2MCl→2M↓+Cl₂↑

[0403] The gases and the etching products that have not been involved inthe reactions are exhausted through an exhaust port 27.

[0404] The source gas has been described, with the Cl₂ gas diluted with,say, He or Ar taken as an example. However, the Cl₂ gas can be usedalone, or an HCl gas can also be applied. If the HCl gas is applied, anHCl gas plasma is generated as the source gas plasma. Thus, the sourcegas may be any gas containing chlorine, and a gas mixture of an HCl gasand a Cl₂ gas is also usable. As the material for the metal member 7, itis possible to use an industrially applicable metal such as Ag, Au, Ptor Si.

[0405] The substrate 3, on which the barrier metal film 26 has beenformed, is subjected to a film forming device, which forms a thin copper(Cu) film or a thin aluminum (Al) film on the barrier metal film 26.Because of the presence of the barrier metal film 26, there ariseadvantages, for example, such that the thin MN film 24 eliminatesdiffusion of Cu into the substrate 3, and the thin M film 25 ensuresadhesion of Cu.

[0406] If the material to be formed as a film is a materialunproblematic in terms of adhesion (e.g., Al), or if it is a metal towhich the nitride can retain adhesion, the thin M film 25 can be omittedfrom the barrier metal film 26. Furthermore, the reduction reaction iscaused by the temperature difference. However, a reducing gas plasma canbe generated separately to produce a reduction reaction.

[0407] With the above-described barrier metal film production apparatus,the metal is formed by plasmas to produce the barrier metal film 26.Thus, the barrier metal film 26 can be formed uniformly to a smallthickness. Consequently, the barrier metal film 26 can be formed highlyaccurately at a high speed with excellent burial properties in a verysmall thickness even to the interior of a tiny depression, for exampleseveral hundred nanometers wide, which has been provided in thesubstrate 3.

[0408] A barrier metal film production apparatus and a barrier metalfilm production method according to the second embodiment of the presentinvention will be described with reference to FIGS. 3 to 5. FIG. 3 is aschematic side view of the barrier metal film production apparatusaccording to the second embodiment of the present invention. FIG. 4 is aview taken along the arrowed line IV-IV of FIG. 3. FIG. 5 is a viewtaken along the arrowed line V-V of FIG. 4. The same members as themembers illustrated in FIG. 1 are assigned the same numerals, andduplicate explanations are omitted.

[0409] An upper surface of the chamber 1 is an opening, which is closedwith a disk-shaped ceiling board 30 made of an insulating material (forexample, a ceramic). An etched member 31 made of a metal (e.g., W, Ti,Ta or TiSi) is interposed between the opening at the upper surface ofthe chamber 1 and the ceiling board 30. The etched member 31 is providedwith a ring portion 32 fitted into the opening at the upper surface ofthe chamber 1. A plurality of (12 in the illustrated embodiment)protrusions 33, which extend close to the center in the diametricaldirection of the chamber 1 and have the same width, are provided in thecircumferential direction on the inner periphery of the ring portion 32.

[0410] The protrusions 33 are integrally or removably attached to thering portion 32. Notches (spaces) 35 formed between the protrusions 33are present between the ceiling board 30 and the interior of the chamber1. The ring portion 32 is earthed, and the plural protrusions 33 areelectrically connected together and maintained at the same potential.Temperature control means (not shown), such as a heater, is provided inthe etched member 31 to control the temperature of the etched member 31to 200 to 400° C., for example.

[0411] Second protrusions shorter in the diametrical direction than theprotrusions 33 can be arranged between the protrusions 33. Moreover,short protrusions can be arranged between the protrusion 33 and thesecond protrusion. By so doing, the area of copper, an object to beetched, can be secured, with an induced current being suppressed.

[0412] A planar winding-shaped plasma antenna 34, for converting theatmosphere inside the chamber 1 into a plasma, is provided above theceiling board 30. The plasma antenna 34 is formed in a planar ring shapeparallel to the surface of the ceiling board 30. A matching instrument10 and a power source 11 are connected to the plasma antenna 34 tosupply power. The etched member 31 has the plurality of protrusions 33provided in the circumferential direction on the inner periphery of thering portion 32, and includes the notches (spaces) 35 formed between theprotrusions 33. Thus, the protrusions 33 are arranged between thesubstrate 3 and the ceiling board 30 in a discontinuous state relativeto the flowing direction of electricity in the plasma antenna 34.

[0413] With the above-described barrier metal film production apparatus,the source gas is supplied through the nozzles 12 to the interior of thechamber 1, and electromagnetic waves are shot from the plasma antenna 34into the chamber 1. As a result, the Cl₂ gas is ionized to generate aCl₂ gas plasma (source gas plasma) 21. The etched member 31, an electricconductor, is present below the plasma antenna 34. However, the Cl₂ gasplasma 21 occurs stably between the etched member 31 and the substrate3, namely, below the etched member 31, under the following action:

[0414] The action by which the Cl₂ gas plasma 21 is generated below theetched member 31 will be described. As shown in FIG. 5, a flow A ofelectricity in the plasma antenna 34 of the planar ring shape crossesthe protrusions 33. At this time, an induced current B occurs on thesurface of the protrusion 33 opposed to the plasma antenna 34. Since thenotches (spaces) 35 are present in the etched member 31, the inducedcurrent B flows onto the lower surface of each protrusion 33, forming aflow a in the same direction as the flow A of electricity in the plasmaantenna 34 (Faraday shield).

[0415] When the etched member 31 is viewed from the substrate 3,therefore, there is no flow in a direction in which the flow A ofelectricity in the plasma antenna 34 is canceled out. Furthermore, thering portion 32 is earthed, and the protrusions 33 are maintained at thesame potential. Thus, even though the etched member 31, an electricconductor, exists, the electromagnetic wave is reliably thrown from theplasma antenna 34 into the chamber 1. Consequently, the Cl₂ gas plasma21 is stably generated below the etched member 31.

[0416] Furthermore, plasma generation means composed of a passage 15, anexcitation chamber 16 and a plasma antenna 17 is provided above thesupport platform 2.

[0417] The Cl₂ gas plasma 21 causes an etching reaction to the etchedmember 31, forming a precursor (M_(x)Cl_(y): M is a metal such as W, Ti,Ta or TiSi) 22. In the excitation chamber 16, the NH₃ gas is ionized togenerate an NH₃ gas plasma 23. The excited ammonia of the NH₃ gas plasma23 in the excitation chamber 16 is fed to the precursor (M_(x)Cl_(y)) 22inside the chamber 1 through the opening portion 14. Because of thisconstruction, the metal component of the precursor (M_(x)Cl_(y)) 22 andammonia react to form a metal nitride (MN) (formation means). At thistime, the etched member 31 and the excitation chamber 16 are maintainedby the plasmas at predetermined temperatures (e.g., 200 to 400° C.)which are higher than the temperature of the substrate 3.

[0418] The metal nitride (MN) formed within the chamber 1 is transportedtoward the substrate 3 controlled to a low temperature, whereby a thinMN film 24 is formed on the surface of the substrate 3. After the thinMN film 24 is formed, the supply of the NH₃ gas and the supply of powerto the power source 19 are cut off. Thus, the precursor (M_(x)Cl_(y)) 22is transported toward the substrate 3 controlled to a lower temperaturethan the temperature of the etched member 31. The precursor(M_(x)Cl_(y)) 22 transported toward the substrate 3 is converted intoonly metal (M) ions by a reduction reaction, and directed at thesubstrate 3 to form a thin M film 25 on the thin MN film 24 on thesubstrate 3. A barrier metal film 26 is composed of the thin MN film 24and the thin M film 25 (see FIG. 2). The gases and the etching products,which have not been involved in the reactions, are exhausted through anexhaust port 27.

[0419] With the above-described barrier metal film production apparatus,similar to the first embodiment, the metal is formed by plasmas toproduce the barrier metal film 26. Thus, the barrier metal film 26 canbe formed uniformly to a small thickness. Consequently, the barriermetal film 26 can be formed highly accurately at a high speed withexcellent burial properties in a very small thickness even to theinterior of a tiny depression, for example several hundred nanometerswide, which has been provided in the substrate 3.

[0420] In addition, the etched member 31 has the plurality ofprotrusions 33 provided in the circumferential direction on the innerperiphery of the ring portion 32, and includes the notches (spaces) 35formed between the protrusions 33. Thus, the induced currents generatedin the etched member 31 flow in the same direction as the flowingdirection of electricity in the plasma antenna 34, when viewed from thesubstrate 3. Therefore, even though the etched member 31, an electricconductor, exists below the plasma antenna 34, the electromagnetic wavesare reliably thrown from the plasma antenna 34 into the chamber 1.Consequently, the Cl₂ gas plasma 21 can be stably generated below theetched member 31.

[0421] A barrier metal film production apparatus and a barrier metalfilm production method according to the third embodiment of the presentinvention will be described with reference to FIG. 6. FIG. 6 is aschematic side view of the barrier metal film production apparatusaccording to the third embodiment of the present invention. The samemembers as the members illustrated in FIGS. 1 and 3 are assigned thesame numerals, and duplicate explanations are omitted.

[0422] The opening of an upper portion of the chamber 1 is closed with aceiling board 30, for example, made of a ceramic (an insulatingmaterial). An etched member 41 made of a metal (e.g., W, Ti, Ta or TiSi)is provided on a lower surface of the ceiling board 30, and the etchedmember 41 is of a quadrangular pyramidal shape. Slit-shaped secondopening portions 42 are formed at a plurality of locations (for example,four locations) in the periphery of an upper part of the cylindricalportion of the chamber 1, and one end of a tubular second passage 43 isfixed to the second opening portion 42.

[0423] A tubular second excitation chamber 44 made of an insulator isprovided halfway through the second passage 43, and a coiled secondplasma antenna 45 is provided around the second excitation chamber 44.The plasma antenna 45 is connected to a matching instrument 48 and apower source 49 to receive power. The second plasma antenna 45, thematching instrument 48 and the power source 49 constitute plasmageneration means.

[0424] A flow controller 46 is connected to the other end of the secondpassage 43, and a chlorine-containing source gas (a Cl₂ gas diluted withHe or Ar to a chlorine concentration of ≦50%, preferably about 10%) issupplied into the passage 43 via the flow controller 46. By shootingelectromagnetic waves from the second plasma antenna 45 into the secondexcitation chamber 44, the Cl₂ gas is ionized to generate a Cl₂ gasplasma (source gas plasma) 47. Because of the generation of the Cl₂ gasplasma 47, excited chlorine is fed into the chamber 1 through the secondopening portion 42, whereupon the etched member 41 is etched withexcited chlorine.

[0425] With the above-described barrier metal film production apparatus,the source gas is supplied into the second passage 43 via the flowcontroller 46 and fed into the second excitation chamber 44. By shootingelectromagnetic waves from the second plasma antenna 45 into the secondexcitation chamber 44, the Cl₂ gas is ionized to generate a Cl₂ gasplasma (source gas plasma) 47. Since a predetermined differentialpressure has been established between the pressure inside the chamber 1and the pressure inside the second excitation chamber 44 by the vacuumdevice 8, the excited chlorine of the Cl₂ gas plasma 47 in the secondexcitation chamber 44 is fed to the etched member 41 inside the chamber1 through the second opening portion 42. The excited chlorine causes anetching reaction to the etched member 41, forming a precursor(M_(x)Cl_(y)) 22 inside the chamber 1. At this time, the etched member41 is maintained at a predetermined temperature (e.g., 200 to 400° C.),which is higher than the temperature of the substrate 3, by a heater 50provided in the ceiling board 30.

[0426] In the excitation chamber 16, the NH₃ gas is ionized to generatean NH₃ gas plasma 23. The excited ammonia of the NH₃ gas plasma 23 inthe excitation chamber 16 is fed to the precursor (M_(x)Cl_(y)) 22inside the chamber 1 through the opening portion 14. As a result, themetal component of the precursor (M_(x)Cl_(y)) 22 and ammonia react toform a metal nitride (MN). At this time, the excitation chamber 16 ismaintained by the plasma at a predetermined temperature (e.g., 200 to400° C.) which is higher than the temperature of the substrate 3.

[0427] The metal nitride (MN) formed within the chamber 1 is transportedtoward the substrate 3 controlled to a low temperature, whereby a thinMN film 24 is formed on the surface of the substrate 3. After the thinMN film 24 is formed, the supply of the NH₃ gas and the supply of powerto the power source 19 are cut off. Thus, the precursor (M_(x)Cl_(y)) 22is transported toward the substrate 3 controlled to a lower temperaturethan the temperature of the etched member 41. The precursor(M_(x)Cl_(y)) 22 transported toward the substrate 3 is converted intoonly metal (M) ions by a reduction reaction, and directed at thesubstrate 3 to form a thin M film 25 on the thin MN film 24 placed onthe substrate 3. A barrier metal film 26 is composed of the thin MN film24 and the thin M film 25 (see FIG. 2). The gases and the etchingproducts that have not been involved in the reactions are exhaustedthrough an exhaust port 27.

[0428] With the above-described barrier metal film production apparatus,similar to the first embodiment and the second embodiment, the metal isformed by plasmas to produce the barrier metal film 26. Thus, thebarrier metal film 26 can be formed uniformly to a small thickness.Consequently, the barrier metal film 26 can be formed highly accuratelyat a high speed with excellent burial properties in a very smallthickness even to the interior of a tiny depression, for example severalhundred nanometers wide, which has been provided in the substrate 3.

[0429] Furthermore, the Cl₂ gas plasma 47 is generated in the secondexcitation chamber 44 isolated from the chamber 1. Thus, the substrate 3is not exposed to the plasma any more, and the substrate 3 becomes freefrom damage from the plasma.

[0430] As the means for generating the Cl₂ gas plasma 47 in the secondexcitation chamber 44, namely, the means for exciting the source gas toconvert it into an excited source gas, it is possible to use microwaves,laser, electron rays, or synchrotron radiation. It is also permissibleto form the precursor by heating the metal filament to a hightemperature. The construction for isolating the Cl₂ gas plasma 47 fromthe substrate 3 may be the provision of the second excitation chamber 44in the passage 43, as stated above, or may be other construction, forexample, the isolation of the chamber 1.

[0431] A barrier metal film production apparatus and a barrier metalfilm production method according to the fourth embodiment of the presentinvention will be described with reference to FIG. 7. FIG. 7 is aschematic side view of a barrier metal film production apparatusaccording to the fourth embodiment of the present invention. The samemembers as the members illustrated in FIG. 1 are assigned the samenumerals, and duplicate explanations are omitted.

[0432] Compared with the barrier metal film production apparatus of thefirst embodiment shown in FIG. 1, the plasma antenna 9 is not providedaround the cylindrical portion of the chamber 1, and the matchinginstrument 10 and power source 11 are connected to the metal member 7for supply of power to the metal member 7.

[0433] With the above-described barrier metal film production apparatus,the source gas is supplied from the nozzle 12 into the chamber 1, andelectromagnetic waves are shot from the metal member 7 into the chamber1, whereby the Cl₂ gas is ionized to generate a Cl₂ gas plasma (sourcegas plasma) 21. The Cl₂ gas plasma 21 causes an etching reaction to themetal member 7, forming a precursor (M_(x)Cl_(y)) 22. At this time, themetal member 7 is maintained at a temperature (e.g., 200 to 400° C.),which is higher than the temperature of the substrate 3, by temperaturecontrol means (not shown).

[0434] In the excitation chamber 16, the NH₃ gas is ionized to generatean NH₃ gas plasma 23. The excited ammonia of the NH₃ gas plasma 23 inthe excitation chamber 16 is fed to the precursor (M_(x)Cl_(y)) 22inside the chamber 1 through the opening portion 14. As a result, themetal component of the precursor (M_(x)Cl_(y)) 22 and ammonia react toform a metal nitride (MN). At this time, the excitation chamber 16 ismaintained by the plasma at a predetermined temperature (e.g., 200 to400° C.) which is higher than the temperature of the substrate 3.

[0435] The metal nitride (MN) formed within the chamber 1 is transportedtoward the substrate 3 controlled to a low temperature, whereby a thinMN film 24 is formed on the surface of the substrate 3. After the thinMN film 24 is formed, the supply of the NH₃ gas and the supply of powerto the power source 19 are cut off. Thus, the precursor (M_(x)Cl_(y)) 22is transported toward the substrate 3 controlled to a lower temperaturethan the temperature of the metal member 7. The precursor (M_(x)Cl_(y))22 transported toward the substrate 3 is converted into only metal (M)ions by a reduction reaction, and directed at the substrate 3 to form athin M film 25 on the thin MN film 24 placed on the substrate 3. Abarrier metal film 26 is composed of the thin MN film 24 and the thin Mfilm 25 (see FIG. 2). The gases and the etching products that have notbeen involved in the reactions are exhausted through an exhaust port 27.

[0436] With the above-described barrier metal film production apparatus,similar to the first embodiment to the third embodiment, the metal isformed by plasmas to produce the barrier metal film 26. Thus, thebarrier metal film 26 can be formed uniformly to a small thickness.Consequently, the barrier metal film 26 can be formed highly accuratelyat a high speed with excellent burial properties in a very smallthickness even to the interior of a tiny depression, for example severalhundred nanometers wide, which has been provided in the substrate 3.

[0437] Furthermore, the metal member 7 itself is applied as an electrodefor plasma generation. Thus, the plasma antenna 9 need not be providedaround the cylindrical portion of the chamber 1, and the degree offreedom of the construction in the surroundings can be increased.

[0438] A barrier metal film production apparatus and a barrier metalfilm production method according to the fifth embodiment of the presentinvention will be described with reference to FIG. 8. FIG. 8 is aschematic side view of the barrier metal film production apparatusaccording to the fifth embodiment of the present invention. The samemembers as the members illustrated in FIG. 1 are assigned the samenumerals, and duplicate explanations are omitted.

[0439] Compared with the first embodiment shown in FIG. 1, the barriermetal film production apparatus shown in FIG. 8 lacks the openingportion 14, passage 15, excitation chamber 16, plasma antenna 17,matching instrument 18, power source 19 and flow controller 20. Nozzles12 for supplying a gas mixture of a source gas (Cl₂ gas) and a nitrogengas (N₂ gas) as a nitrogen-containing gas to the interior of the chamber1 are connected to the cylindrical portion of the chamber 1. The Cl₂ gasand the N₂ gas are mixed in a mixed gas flow controller 81, and the gasmixture of the Cl₂ gas and the N₂ gas is supplied to the nozzle 12 viathe mixed gas flow controller 81. Other constructions are the same as inthe first embodiment.

[0440] With the above-described barrier metal film production apparatus,the mixed gas comprising the Cl₂ gas and the N₂ gas is supplied throughthe nozzles 12 to the interior of the chamber 1, and electromagneticwaves are shot from the plasma antenna 9 into the chamber 1. As aresult, the Cl₂ gas and the N₂ gas are ionized to generate a Cl₂ gas/N₂gas plasma 82. The Cl₂ gas/N₂ gas plasma 82 causes an etching reactionto the metal member 7, forming a precursor (M_(x)Cl_(y): M is a metalsuch as W, Ti, Ta or TiSi) 22. Also, the precursor 22 and N₂ react toform a metal nitride (MN). At this time, the metal member 7 ismaintained by the plasma (or temperature control means (not shown)) at apredetermined temperature (e.g., 200 to 400° C.) which is higher thanthe temperature of the substrate 3.

[0441] The metal nitride (MN) formed within the chamber 1 is transportedtoward the substrate 3 controlled to a low temperature, whereby a thinMN film 24 is formed on the surface of the substrate 3. After the thinMN film 24 is formed, the supply of the N₂ gas to the mixed gas flowcontroller 81 is cut off. Thus, the precursor (M_(x)Cl_(y)) 22 istransported toward the substrate 3 controlled to a lower temperaturethan the temperature of the metal member 7. The precursor (M_(x)Cl_(y))22 transported toward the substrate 3 is converted into only metal (M)ions by a reduction reaction, and directed at the substrate 3 to form athin M film 25 on the surface of the substrate 3. A barrier metal film26 is composed of the thin MN film 24 and the thin M film 25 (see FIG.2).

[0442] The substrate 3, on which the barrier metal film 26 has beenformed, is to have a thin copper (Cu) film or a thin aluminum (Al) filmformed on the barrier metal film 26 by a film forming device. Because ofthe presence of the barrier metal film 26, there arise advantages, forexample, such that the thin MN film 24 eliminates diffusion of Cu intothe substrate 3, and the thin M film 25 ensures adhesion of Cu.

[0443] If the material to be formed as a film is a materialunproblematic in terms of adhesion (e.g., Al), or if it is a metal towhich the nitride can retain adhesion, the thin M film 25 can be omittedfrom the barrier metal film 26.

[0444] With the above-described barrier metal film production apparatus,the same effects as in the first embodiment are obtained. In addition,the supply line for the gases can be simplified, and the number of theplasma sources can be decreased. Thus, the cost of the product can bereduced.

[0445] The sixth embodiment of a barrier metal film production apparatusand a barrier metal film production method according to the presentinvention will be described with reference to FIG. 9. FIG. 9 is aschematic side view of the barrier metal film production apparatusaccording to the sixth embodiment of the present invention. The samemembers as in the second and fifth embodiments illustrated in FIGS. 3 to5 and 8 are assigned the same numerals, and duplicate explanations areomitted.

[0446] Compared with the second embodiment shown in FIG. 3, the barriermetal film production apparatus shown in FIG. 9 lacks the openingportion 14, passage 15, excitation chamber 16, plasma antenna 17,matching instrument 18, power source 19 and flow controller 20. Nozzles12 for supplying a gas mixture of a source gas (Cl₂ gas) and a nitrogengas (N₂ gas) as a nitrogen-containing gas to the interior of the chamber1 are connected to the cylindrical portion of the chamber 1. The Cl₂ gasand the N₂ gas are mixed in a mixed gas flow controller 81, and the gasmixture of the Cl₂ gas and the N₂ gas is supplied to the nozzle 12 viathe mixed gas flow controller 81. Other constructions are the same as inthe second embodiment.

[0447] With the above-described barrier metal film production apparatus,the mixed gas comprising the Cl₂ gas and the N₂ gas is supplied throughthe nozzles 12 to the interior of the chamber 1, and electromagneticwaves are shot from the plasma antenna 34 into the chamber 1. As aresult, the Cl₂ gas and the N₂ gas are ionized to generate a Cl₂ gas/N₂gas plasma 82. The etched member 31, an electric conductor, is presentbelow the plasma antenna 34. As stated earlier, however, the Cl₂ gas/N₂gas plasma 82 occurs stably between the etched member 31 and thesubstrate 3, namely, below the etched member 31.

[0448] The Cl₂ gas/N₂ gas plasma 82 causes an etching reaction to theetched member 31, forming a precursor (M_(x)Cl_(y): M is a metal such asW, Ti, Ta or TiSi) 22. Also, the precursor 22 and N₂ react to form ametal nitride (MN). At this time, the etched member 31 is maintained bythe plasma (or temperature control means (not shown)) at a predeterminedtemperature (e.g., 200 to 400° C.) which is higher than the temperatureof the substrate 3.

[0449] The metal nitride (MN) formed within the chamber 1 is transportedtoward the substrate 3 controlled to a low temperature, whereby a thinMN film 24 is formed on the surface of the substrate 3. After the thinMN film 24 is formed, the supply of the N₂ gas to the mixed gas flowcontroller 81 is cut off. Thus, the precursor (M_(x)Cl_(y)) 22 istransported toward the substrate 3 controlled to a lower temperaturethan the temperature of the etched member 31. The precursor(M_(x)Cl_(y)) 22 transported toward the substrate 3 is converted intoonly metal (M) ions by a reduction reaction, and directed at thesubstrate 3 to form a thin M film 25 on the thin MN film 24 on thesubstrate 3. A barrier metal film 26 is composed of the thin MN film 24and the thin M film 25 (see FIG. 2).

[0450] The substrate 3, on which the barrier metal film 26 has beenformed, is to have a thin copper (Cu) film or a thin aluminum (Al) filmformed on the barrier metal film 26 by a film forming device. Because ofthe presence of the barrier metal film 26, there arise advantages, forexample, such that the thin MN film 24 eliminates diffusion of Cu intothe substrate 3, and the thin M film 25 ensures adhesion of Cu.

[0451] If the material to be formed as a film is a materialunproblematic in terms of adhesion (e.g., Al), or if it is a metal towhich the nitride can retain adhesion, the thin M film 25 can be omittedfrom the barrier metal film 26.

[0452] With the above-described barrier metal film production apparatus,the same effects as in the second embodiment are obtained. In addition,the supply line for the gases can be simplified, and the number of theplasma sources can be decreased. Thus, the cost of the product can bereduced.

[0453] The seventh embodiment of a barrier metal film productionapparatus and a barrier metal film production method according to thepresent invention will be described with reference to FIG. 10. FIG. 10is a schematic side view of the barrier metal film production apparatusaccording to the seventh embodiment of the present invention. The samemembers as in the third and fifth embodiments illustrated in FIGS. 6 and8 are assigned the same numerals, and duplicate explanations areomitted.

[0454] Compared with the third embodiment shown in FIG. 6, the barriermetal film production apparatus shown in FIG. 10 lacks the openingportion 14, passage 15, excitation chamber 16, plasma antenna 17,matching instrument 18, power source 19 and flow controller 20. A gasmixture of a source gas (Cl₂ gas) and a nitrogen gas (N₂ gas) as anitrogen-containing gas is supplied from a mixed gas flow controller 81to a second excitation chamber 44. Other constructions are the same asin the third embodiment.

[0455] With the above-described barrier metal film production apparatus,the mixed gas comprising the Cl₂ gas and the N₂ gas is supplied into asecond passage 43 via the mixed gas flow controller 81, and fed into thesecond excitation chamber 44. Electromagnetic waves are shot from asecond plasma antenna 45 into the second excitation chamber 44. As aresult, the Cl₂ gas and the N₂ gas are ionized to generate a Cl₂ gas/N₂gas plasma 82. Since a predetermined differential pressure has beenestablished between the pressure inside the chamber 1 and the pressureinside the second excitation chamber 44 by the vacuum device 8, theexcited chlorine and excited nitrogen of the Cl₂ gas/N₂ gas plasma 82 inthe second excitation chamber 44 are fed to the etched member 41 insidethe chamber 1 through the second opening portion 42. The excitedchlorine causes an etching reaction to the etched member 41, forming aprecursor (M_(x)Cl_(y)) 22 inside the chamber 1. Also, the precursor 22and the excited nitrogen react to form a metal nitride (MN). At thistime, the etched member 41 is maintained at a predetermined temperature(e.g., 200 to 400° C.), which is higher than the temperature of thesubstrate 3, by a heater 50 provided in a ceiling board 30.

[0456] The metal nitride (MN) formed within the chamber 1 is transportedtoward the substrate 3 controlled to a low temperature, whereby a thinMN film 24 is formed on the surface of the substrate 3. After the thinMN film 24 is formed, the supply of the N₂ gas to the mixed gas flowcontroller 81 is cut off. Thus, the precursor (M_(x)Cl_(y)) 22 istransported toward the substrate 3 controlled to a lower temperaturethan the temperature of the etched member 41. The precursor(M_(x)Cl_(y)) 22 transported toward the substrate 3 is converted intoonly metal (M) ions by a reduction reaction, and directed at thesubstrate 3 to form a thin M film 25 on the thin MN film 24 on thesubstrate 3. A barrier metal film 26 is composed of the thin MN film 24and the thin M film 25 (see FIG. 2).

[0457] The substrate 3, on which the barrier metal film 26 has beenformed, is to have a thin copper (Cu) film or a thin aluminum (Al) filmformed on the barrier metal film 26 by a film forming device. Because ofthe presence of the barrier metal film 26, there arise advantages, forexample, such that the thin MN film 24 eliminates diffusion of Cu intothe substrate 3, and the thin M film 25 ensures adhesion of Cu.

[0458] If the material to be formed as a film is a materialunproblematic in terms of adhesion (e.g., Al), or if it is a metal towhich the nitride can retain adhesion, the thin M film 25 can be omittedfrom the barrier metal film 26.

[0459] With the above-described barrier metal film production apparatus,the same effects as in the third embodiment are obtained. In addition,the supply line for the gases can be simplified, and the number of theplasma sources can be decreased. Thus, the cost of the product can bereduced.

[0460] The eighth embodiment of a barrier metal film productionapparatus and a barrier metal film production method according to thepresent invention will be described with reference to FIG. 11. FIG. 11is a schematic side view of the barrier metal film production apparatusaccording to the eighth embodiment of the present invention. The samemembers as in the fourth embodiment and the fifth embodiment illustratedin FIGS. 7 and 8 are assigned the same numerals, and duplicateexplanations are omitted.

[0461] Compared with the fourth embodiment shown in FIG. 7, the barriermetal film production apparatus shown in FIG. 11 lacks the openingportion 14, passage 15, excitation chamber 16, plasma antenna 17,matching instrument 18, power source 19 and flow controller 20. Nozzles12 for supplying a gas mixture of a source gas (Cl₂ gas) and a nitrogengas (N₂ gas) as a nitrogen-containing gas to the interior of the chamber1 are connected to the cylindrical portion of the chamber 1. The Cl₂ gasand the N₂ gas are mixed in a mixed gas flow controller 81, and the gasmixture of the Cl₂ gas and the N₂ gas is supplied to the nozzle 12 viathe mixed gas flow controller 81. Other constructions are the same as inthe fourth embodiment.

[0462] With the above-described barrier metal film production apparatus,the mixed gas comprising the Cl₂ gas and the N₂ gas is supplied throughthe nozzles 12 to the interior of the chamber 1, and electromagneticwaves are shot from the metal member 7 into the chamber 1. As a result,the Cl₂ gas and the N₂ gas are ionized to generate a Cl₂ gas/N₂ gasplasma 82. The Cl₂ gas/N₂ gas plasma 82 causes an etching reaction tothe metal member 7, forming a precursor (M_(x)Cl_(y): M is a metal suchas W, Ti, Ta or TiSi) 22. Also, the precursor 22 and N₂ react to form ametal nitride (MN). At this time, the metal member 7 is maintained bythe plasma (or temperature control means (not shown)) at a predeterminedtemperature (e.g., 200 to 400° C.) which is higher than the temperatureof the substrate 3.

[0463] The metal nitride (MN) formed within the chamber 1 is transportedtoward the substrate 3 controlled to a low temperature, whereby a thinMN film 24 is formed on the surface of the substrate 3. After the thinMN film 24 is formed, the supply of the N₂ gas to the mixed gas flowcontroller 81 is cut off. Thus, the precursor (M_(x)Cl_(y)) 22 istransported toward the substrate 3 controlled to a lower temperaturethan the temperature of the metal member 7. The precursor (M_(x)Cl_(y))22 transported toward the substrate 3 is converted into only metal (M)ions by a reduction reaction, and directed at the substrate 3 to form athin M film 25 on the thin MN film 24 on the substrate 3. A barriermetal film 26 is composed of the thin MN film 24 and the thin M film 25(see FIG. 2).

[0464] The substrate 3, on which the barrier metal film 26 has beenformed, is to have a thin copper (Cu) film or a thin aluminum (Al) filmformed on the barrier metal film 26 by a film forming device. Because ofthe presence of the barrier metal film 26, there arise advantages, forexample, such that the thin MN film 24 eliminates diffusion of Cu intothe substrate 3, and the thin M film 25 ensures adhesion of Cu.

[0465] If the material to be formed as a film is a materialunproblematic in terms of adhesion (e.g., Al), or if it is a metal towhich the nitride can retain adhesion, the thin M film 25 can be omittedfrom the barrier metal film 26.

[0466] With the above-described barrier metal film production apparatus,the same effects as in the fourth embodiment are obtained. In addition,the supply line for the gases can be simplified, and the number of theplasma sources can be decreased. Thus, the cost of the product can bereduced.

[0467] In the foregoing fifth to eighth embodiments, the N₂ gas is mixedwith the Cl₂ gas in the mixed gas flow controller 81, and the gasmixture is supplied into the chamber 1. However, the N₂ gas and the Cl₂gas can be supplied through separate nozzles. Also, ammonia can beapplied as the nitrogen-containing gas.

[0468] The ninth embodiment of the barrier metal film productionapparatus and barrier metal film production method of the presentinvention will be described with reference to FIGS. 12 and 18. FIG. 12is a schematic side view of the barrier metal film production apparatusaccording to the ninth embodiment of the present invention. FIG. 13shows the sectional status of a substrate illustrating a barrier metalfilm. FIGS. 14 and 15 show the concept status of a barrier metal film indenitrification. FIG. 16 shows the concept status of a barrier metalfilm in oxide layer formation. FIG. 17 represents the relationshipbetween the contact angle of copper particles and the oxygenconcentration of the substrate. FIG. 18 shows the concept status of abarrier metal film in hydroxyl group formation. FIG. 19 schematicallyshows a construction illustrating another example of diluent gas supplymeans.

[0469] As shown in FIG. 12, a support platform 102 is provided near thebottom of a cylindrical chamber 101 made of, say, a ceramic (aninsulating material), and a substrate 103 is placed on the supportplatform 102. Temperature control means 106, as control means, equippedwith a heater 104 and refrigerant flow-through means 105 is provided inthe support platform 102 so that the support platform 102 is controlledto a predetermined temperature (for example, a temperature at which thesubstrate 103 is maintained at 100 to 200° C.) by the temperaturecontrol means 106.

[0470] An upper surface of the chamber 101 is an opening, which isclosed with a metal member 107, as an etched member, made of a metal(e.g., W, Ti, Ta, or TiSi). The interior of the chamber 101 closed withthe metal member 107 is maintained at a predetermined pressure by avacuum device 108. A plasma antenna 109, as a coiled winding antenna ofplasma generation means, is provided around a cylindrical portion of thechamber 101. A matching instrument 110 and a power source 111 areconnected to the plasma antenna 109 to supply power.

[0471] A nozzle 112, as source gas supply means, for supplying a sourcegas (a Cl₂ gas diluted with He or Ar to a chlorine concentration of ≦50%, preferably about 10%), containing chlorine as a halogen, to theinterior of the chamber 101 is connected to the cylindrical portion ofthe chamber 101 below the metal member 107. The nozzle 112 is fed withthe source gas via a flow controller 113. The source gas is suppliedfrom the nozzle 112, and electromagnetic waves are shot from the plasmaantenna 109 into the chamber 101, whereby the Cl₂ gas is ionized togenerate a Cl₂ gas plasma (plasma generation means). Fluorine (F),bromine (Br) or iodine (I) can also be applied as the halogen to beincorporated into the source gas.

[0472] A nozzle 114, as nitrogen-containing gas supply means, forsupplying an ammonia gas (NH₃ gas) as a nitrogen-containing gas, to theinterior of the chamber 101 is connected to the cylindrical portion ofthe chamber 101 below the metal member 107. The NH₃ gas is supplied fromthe nozzle 114, and electromagnetic waves are shot from the plasmaantenna 109 into the chamber 101, whereby the NH₃ gas is ionized togenerate an NH₃ gas plasma (plasma generation means).

[0473] A diluent gas nozzle 121 is provided, as diluent gas supplymeans, for supplying an Ar gas as a diluent gas, to the interior of thechamber 101 above the surface of the substrate 103. The Ar gas issupplied from the diluent gas nozzle 121, and electromagnetic waves areshot from the plasma antenna 109 into the chamber 101, whereby the Argas is ionized to generate an Ar gas plasma (surface treatment plasmageneration means).

[0474] As described above, the diluent gas supply means applies the Argas as the diluent gas for the Cl₂ gas. In this case, as shown in FIG.19, a control valve 122 may be provided at the site of merger betweenthe source gas (Cl₂ gas) and the diluent gas (Ar gas) so that the Cl₂gas is stopped during generation of the Ar gas plasma, and only the Argas is supplied through the nozzle 112. According to this construction,there is no need for the provision of the diluent gas nozzle 121,presenting advantage in space.

[0475] An oxygen gas nozzle 115 is provided, as oxygen gas supply means,for supplying an oxygen gas (O₂ gas) to the interior of the chamber 101above the surface of the substrate 103. The O₂ gas is supplied from theoxygen gas nozzle 115, and electromagnetic waves are shot from theplasma antenna 109 into the chamber 101, whereby the O₂ gas is ionizedto generate an O₂ gas plasma (oxygen plasma generation means).

[0476] Furthermore, a hydrogen gas nozzle 116 is provided, as hydrogengas supply means, for supplying a hydrogen gas (H₂ gas) to the interiorof the chamber 101 above the surface of the substrate 103. The H₂ gas issupplied from the hydrogen gas nozzle 116, and electromagnetic waves areshot from the plasma antenna 109 into the chamber 101, whereby the H₂gas is ionized to generate an H₂ gas plasma (hydroxyl group plasmageneration means).

[0477] With the above-described barrier metal film production apparatus,the source gas is supplied through the nozzle 112 to the interior of thechamber 101, and electromagnetic waves are shot from the plasma antenna109 into the chamber 101. As a result, the Cl₂ gas is ionized togenerate a Cl₂ gas plasma (source gas plasma). The Cl₂ gas plasma causesan etching reaction to the metal member 107, forming a precursor(M_(x)Cl_(y): M is a metal such as W, Ti, Ta or TiSi) 120. The metalmember 107 is maintained by the plasma at a predetermined temperature(e.g., 200 to 400° C.) which is higher than the temperature of thesubstrate 103.

[0478] Also, the NH₃ gas is supplied into the chamber 101 through thenozzle 114, and electromagnetic waves are shot from the plasma antenna109 into the chamber 101. Thus, the NH₃ gas is ionized to generate anNH₃ gas plasma, which causes a reduction reaction with the precursor120, forming a metal nitride (MN). The metal nitride (MN) formed withinthe chamber 101 is transported toward the substrate 103 controlled to alow temperature, whereupon MN is formed into a film on the surface ofthe substrate 103 to produce a barrier metal film 123 (see FIG. 13).

[0479] The reaction for formation of the barrier metal film 123 can beexpressed by:

2MCl+2NH₃→2MN↓+HCl↑+2H₂↑

[0480] The gases and the etching products that have not been involved inthe reaction are exhausted through an exhaust port 117.

[0481] After the barrier metal film 1123 has been formed, the Ar gas issupplied from the diluent gas nozzle 121, and electromagnetic waves areshot from the plasma antenna 109 into the chamber 101, therebygenerating an Ar gas plasma. On the surface of the substrate 103, thebarrier metal film 123 of MN has been formed, as shown in FIG. 14. Thus,upon generation of the Ar gas plasma, Ar⁺ etches the barrier metal film123 on the surface of the substrate 103, thereby performing a treatmentfor removing the nitrogen atoms (N) of the MN in the superficial layerto decrease the nitrogen content of the superficial layer relative tothe interior of the matrix of the barrier metal film 123(denitrification).

[0482] As shown in FIG. 14, the barrier metal film 123 comprises M and Nin an amorphous state. In this state, N of a lower mass ispreferentially removed by Ar⁺, so that the superficial layer of thebarrier metal film 123 (for example, up to a half, preferably about athird, of the entire film thickness) is denitrified. As a result, thereemerges the barrier metal film 123 of a two-layer structure, a metallayer 123 a substantially composed of M, and an MN layer 123 b, as shownin FIG. 15. On this occasion, the entire film thickness of the barriermetal film 123 remains the film thickness having the single layer.

[0483] Immediately before formation of the most superficial layer of thebarrier metal film 123 is completed, a trace amount of O₂ gas issupplied through the oxygen gas nozzle 115 into the chamber 101. At thesame time, electromagnetic waves are shot from the plasma antenna 109into the chamber 101 to generate an O₂ gas plasma. As a result, an oxidelayer 124 is formed on the surface of the metal layer 123 a composedsubstantially of M, as shown in FIG. 16. Since the oxide layer 124 hasbeen formed, if a metal (e.g., copper) is deposited (formed as a film)on the surface of the barrier metal film 123, wetting with the metal issatisfactory, thus increasing adhesion.

[0484] In detail, it has been confirmed, as shown in FIG. 17, that thehigher the oxygen concentration of the substrate 103, the smaller thecontact angle θ of a copper particle (the angle that takes minimalsurface energy in the presence of a balanced surface tension when thesubstrate is considered to be a solid and copper is deemed to be aliquid). That is, as the oxygen concentration of the substrate 103increases, the copper particle adheres in a collapsed state (a state ofhigh wetting) to the surface of the substrate 103. Hence, the O₂ gasplasma is generated to form the oxide layer 124 on the surface of themetal layer 123 a. By so doing, the oxygen concentration of thesubstrate 103 can be increased, leading to satisfactory wetting with themetal (copper) to be formed as a film.

[0485] After formation of the oxide layer 124 on the surface of themetal layer 123 a, the H₂ gas is supplied from the hydrogen gas nozzle116 into the chamber 101, and electromagnetic waves are shot from theplasma antenna 109 into the chamber 101, thereby generating an H₂ gasplasma. As a result, hydroxyl groups (OH groups) are formed on thesurface of the oxide layer 124, as shown in FIG. 18. These hydroxylgroups increase hydrophilicity, and can further enhance the adhesion ofthe metal (copper) to be formed as a film.

[0486] With the above-described barrier metal film production apparatus,the metal is formed by the plasma to produce the barrier metal film 123.Thus, the barrier metal film 123 can be formed uniformly to a smallthickness. Consequently, the barrier metal film 123 can be formed highlyaccurately at a high speed with excellent burial properties in a verysmall thickness even to the interior of a tiny depression, for exampleseveral hundred nanometers wide, which has been provided in thesubstrate 103.

[0487] Moreover, denitrification of the barrier metal film 123 iscarried out by removing the nitrogen atoms with the Ar gas plasma. Thus,the barrier metal film 123 can be granted the two-layer structure, themetal layer 123 a substantially composed of M, and the MN layer 123 b.In addition, the entire film thickness can remain the film thicknessconstructed from the single layer. Thus, the barrier metal film 123 canbe formed in a two-layer structure without being thickened. Of the twolayers, the metal layer 123 a can retain adhesion to a metal to beformed as a film on the surface thereof, while the MN layer (123 b) canprevent diffusion of the metal. Hence, it becomes possible to producethe barrier metal film which can be formed with good adhesion to themetal to be formed as a film, with diffusion of the metal beingeliminated.

[0488] Besides, the O₂ gas plasma is generated to form the oxide layer124 on the surface of the metal layer 123 a. Thus, when a metal isformed as a film on the surface of the barrier metal film 123, wettingwith the metal is satisfactory, and adhesion of the metal can beincreased. Additionally, the H₂ gas plasma is generated to form hydroxylgroups (OH groups) on the surface of the oxide layer 124. Thus, thehydrophilicity improves, and can further increase the adhesion of themetal to be formed as a film.

[0489] It is permissible to omit the step of generating the H₂ gasplasma to form hydroxyl groups (OH groups) on the surface of the oxidelayer 124. It is also allowable to omit the step of generating the O₂gas plasma to form the oxide layer 124 on the surface of the metal layer123 a.

[0490] The barrier metal film production apparatus and barrier metalfilm production method according to the tenth embodiment of the presentinvention will be described with reference to FIG. 20. FIG. 20schematically shows the construction of the barrier metal filmproduction apparatus according to the tenth embodiment of the presentinvention. The same members as the members shown in FIG. 12 are assignedthe same numerals, and duplicate explanations are omitted. FIG. 21 showsthe concept status of an example of production of a barrier metal filmby the barrier metal film production apparatus according to the tenthembodiment of the present invention.

[0491] Compared with the barrier metal film production apparatus of theninth embodiment shown in FIG. 12, the barrier metal film productionapparatus of the tenth embodiment shown in FIG. 20 lacks the diluent gasnozzle 121. In the ninth embodiment, the Ar gas is supplied from thediluent gas nozzle 121 to generate an Ar gas plasma. Using the Ar gasplasma, Ar⁺ etches the barrier metal film 123 on the surface of thesubstrate 103, thereby performing a treatment for removing the nitrogenatoms (N) of the MN in the superficial layer to decrease the nitrogencontent of the superficial layer relative to the interior of the matrixof the barrier metal film 123 (denitrification). In the present tenthembodiment, on the other hand, when denitrification is to be performed,the O₂ gas is supplied from the oxygen gas nozzle 115 to generate an O₂gas plasma. O₂ ⁺ etches the barrier metal film 123 on the surface of thesubstrate 103, performing denitrification. After denitrification, theamount of the O₂ gas is decreased to form the oxide layer 124 (see FIG.16). Other constructions and actions are the same as in the ninthembodiment.

[0492] The tenth embodiment can decrease the number of the nozzles forsupplying the gases, thus bringing advantage in space.

[0493] In the barrier metal film production apparatus of the tenthembodiment, the O₂ gas plasma can be used only for the formation of theoxide layer 124 (see FIG. 16) without being used for etching. In thiscase, the barrier metal film 123 is only the single layer, MN layer 123b. If the metal to be formed as a film over the substrate 103 is a metalunproblematic in terms of adhesion (such as Al), for example, thetreatment for forming the metal layer 123 a by etching can be omitted.

[0494] In the barrier metal film production apparatus of the tenthembodiment, moreover, the O₂ gas plasma can be used similarly only forthe formation of the oxide layer 124 (see FIG. 16) without being usedfor etching. In this case, however, after the MN layer 123 b is formed,the supply of the NH₃ gas from the nozzle 114 is cut off to terminatethe reaction of the precursor 120 with an NH₃ gas plasma. Then, as shownin FIG. 21, the metal component of the precursor 120 is superposed onthe MN layer 123 b, whereby the met a layer 123 a can be formed.

[0495] The reaction for formation of the metal layer 123 a from themetal component of the precursor 120 can be expressed by:

2MCl→2M↓+Cl₂↑

[0496] The barrier metal film production apparatus and barrier metalfilm production method according to the eleventh embodiment of thepresent invention will be described with reference to FIG. 22. FIG. 22schematically shows the construction of the barrier metal filmproduction apparatus according to the eleventh embodiment of the presentinvention. The same members as in the barrier metal film productionapparatus shown in FIG. 12 are assigned the same numerals, and duplicateexplanations are omitted.

[0497] As shown in FIG. 22, a support platform 102 is provided near thebottom of a chamber 101, and a substrate 103 is placed on the supportplatform 102. Temperature control means 106, as control means, equippedwith a heater 104 and refrigerant flow-through means 105 is provided inthe support platform 102 so that the support platform 102 is controlledto a predetermined temperature (for example, a temperature at which thesubstrate 103 is maintained at 100 to 200° C.) by the temperaturecontrol means 106. An upper surface of the chamber 101 is an opening,which is closed with a metal member 107 (e.g., W, Ti, Ta, or TiSi). Theinterior of the chamber 101 closed with the metal member 107 ismaintained at a predetermined pressure by a vacuum device 108. A plasmaantenna 109 is provided around a cylindrical portion of the chamber 101.A matching instrument 110 and a power source 111 are connected to theplasma antenna 109 to supply power.

[0498] A nozzle 112 for supplying a source gas is connected to thecylindrical portion of the chamber 101 below the metal member 107. Thesource gas is supplied from the nozzle 112, and electromagnetic wavesare shot from the plasma antenna 109 into the chamber 101, whereby theCl₂ gas is ionized to generate a Cl₂ gas plasma (plasma generationmeans).

[0499] A diluent gas nozzle 121 is provided for supplying an Ar gas tothe interior of the chamber 101. Also, electromagnetic waves are shotfrom the plasma antenna 109 into the chamber 101. Thus, the Ar gas isionized to generate an Ar gas plasma (surface treatment plasmageneration means). If an Ar gas is applied as the diluent gas for theCl₂ gas, diluent gas supply means may be constructed, similar to theninth embodiment, such that only the Ar gas is supplied from the nozzle112.

[0500] An oxygen gas nozzle 115 is provided for supplying an oxygen gas(O₂ gas) to the interior of the chamber 101. Also, electromagnetic wavesare shot from the plasma antenna 109 into the chamber 101. Thus, the O₂gas is ionized to generate an O₂ gas plasma (oxygen plasma generationmeans). Moreover, a hydrogen gas nozzle 116 is provided for supplying ahydrogen gas (H₂ gas) to the interior of the chamber 101. Also,electromagnetic waves are shot from the plasma antenna 109 into thechamber 101. Thus, the H₂ gas is ionized to generate an H₂ gas plasma(hydroxyl group plasma generation means).

[0501] Slit-shaped opening portions 131 are formed at a plurality oflocations (for example, four locations; only one of the locations isshown in the drawing) in the periphery of a lower part of thecylindrical portion of the chamber 101, and one end of a tubular passage132 is fixed to the opening portion 131. A tubular excitation chamber 33made of an insulator is provided halfway through the passage 132, and acoiled plasma antenna 134 is provided around the excitation chamber 133.The plasma antenna 134 is connected to a matching instrument 135 and apower source 136 to receive power. The plasma antenna 134, the matchinginstrument 135 and the power source 136 constitute excitation means. Aflow controller 137 is connected to the other end of the passage 132,and an ammonia gas (NH₃ gas) as a nitrogen-containing gas is suppliedinto the passage 132 via the flow controller 137.

[0502] Separately, the NH₃ gas is supplied into the passage 132 via theflow controller 137 and fed into the excitation chamber 133. By shootingelectromagnetic waves from the plasma antenna 134 into the excitationchamber 133, the NH₃ gas is ionized to generate an NH₃ gas plasma 138.Since a predetermined differential pressure has been established betweenthe pressure inside the chamber 101 and the pressure inside theexcitation chamber 133 by the vacuum device 108, the excited ammonia ofthe NH₃ gas plasma 138 in the excitation chamber 133 is fed to theprecursor (M_(x)Cl_(y)) 120 inside the chamber 101 through the openingportion 131.

[0503] That is, excitation means for exciting the nitrogen-containinggas in the excitation chamber 133 isolated from the chamber 101 isconstructed. Because of this construction, the metal component of theprecursor (M_(x)Cl_(y)) 120 and ammonia react to form a metal nitride(MN) (formation means). At this time, the metal member 107 and theexcitation chamber 133 are maintained by the plasmas at predeterminedtemperatures (e.g., 200 to 400° C.) which are higher than thetemperature of the substrate 103.

[0504] With the above-described barrier metal film production apparatus,the source gas is supplied through the nozzle 112 to the interior of thechamber 101, and electromagnetic waves are shot from the plasma antenna109 into the chamber 101. As a result, a Cl₂ gas plasma (source gasplasma) occurs. The Cl₂ gas plasma causes an etching reaction to themetal member 107, forming a precursor (M_(x)Cl_(y)) 120. The metalmember 107 is maintained by the plasma at a predetermined temperature(e.g., 200 to 400° C.) which is higher than the temperature of thesubstrate 103.

[0505] The excited ammonia of the NH₃ gas plasma 138 in the excitationchamber 133 is fed to the precursor (M_(x)Cl_(y)) 120 inside the chamber101 through the opening portion 131. Thus, a metal nitride (MN) isformed inside the chamber 101. The resulting metal nitride (MN) istransported toward the substrate 103 controlled to a low temperature,whereby a barrier metal film 23 is formed on the surface of thesubstrate 103. The gases and the etching products, which have not beeninvolved in the reaction, are exhausted through an exhaust port 117.

[0506] After the barrier metal film 123 is formed, the Ar gas issupplied from the diluent gas nozzle 121, and electromagnetic waves areshot from the plasma antenna 109 into the chamber 101 to generate an Argas plasma. Using the Ar gas plasma, Ar⁺ etches the barrier metal film123 on the surface of the substrate 103, thereby performing a treatmentfor removing the nitrogen atoms (N) of the MN in the superficial layerto decrease the nitrogen content of the superficial layer relative tothe interior of the matrix of the barrier metal film 123(denitrification). As a result, there emerges the barrier metal film 123of a two-layer structure, a metal layer 123 a substantially composed ofM, and an MN layer 123 b (see FIG. 15).

[0507] Immediately before formation of the most superficial layer of thebarrier metal film 123 is completed, a trace amount of O₂ gas issupplied through the oxygen gas nozzle 115 into the chamber 101. At thesame time, electromagnetic waves are shot from the plasma antenna 109into the chamber 101 to generate an O₂ gas plasma. As a result, an oxidelayer 124 is formed on the surface of the metal layer 123 a composedsubstantially of M (see FIG. 16). Since the oxide layer 124 has beenformed, if a metal (e.g., copper) is deposited (formed as a film) on thesurface of the barrier metal film 123, wetting with the metal issatisfactory, thus increasing adhesion.

[0508] After formation of the oxide layer 124 on the surface of themetal layer 123 a, the H₂ gas is supplied from the hydrogen gas nozzle116 into the chamber 101, and electromagnetic waves are shot from theplasma antenna 109 into the chamber 101, thereby generating an H₂ gasplasma. As a result, hydroxyl groups (OH groups) are formed on thesurface of the oxide layer 124 (see FIG. 18). These hydroxyl groupsincrease hydrophilicity, and can further enhance the adhesion of themetal (copper) to be formed as a film.

[0509] With the above-described barrier metal film production apparatus,the barrier metal film 123 can be formed at a high speed with excellentburial properties in a very small thickness, as in the ninth embodiment.In addition, the entire film thickness can remain the film thicknessconstructed from the single layer. In this state, it becomes possible toproduce the barrier metal film which can be formed with good adhesion tothe metal to be formed as a film, with diffusion of the metal beingeliminated.

[0510] Besides, when a metal is formed as a film on the surface of thebarrier metal film 123, wetting with the metal is satisfactory, andadhesion of the metal can be increased. Additionally, the hydrophilicityimproves, and can further increase the adhesion of the metal to beformed as a film.

[0511] Further, the NH₃ gas plasma 138 is generated in the excitationchamber 133 isolated from the chamber 101. Thus, the influence of theNH₃ gas plasma 138 is not exerted on the surface of the substrate 103.

[0512] It is permissible to omit the step of generating the H₂ gasplasma to form hydroxyl groups (OH groups) on the surface of the oxidelayer 124. It is also allowable to omit the step of generating the O₂gas plasma to form the oxide layer 124 on the surface of the metal layer123 a.

[0513] The barrier metal film production apparatus according to theeleventh embodiment shown in FIG. 22 may have a construction in whichthe diluent gas nozzle 121 is not provided. In the eleventh embodiment,the Ar gas is supplied from the diluent gas nozzle 121 to generate an Argas plasma. Ar⁺ etches the barrier metal film 123 on the surface of thesubstrate 103, thereby removing the nitrogen atoms (N) of the MN in thesuperficial layer to decrease the nitrogen content of the superficiallayer relative to the interior of the matrix of the barrier metal film123 (denitrification). When denitrification is to be performed, the O₂gas is supplied from the oxygen gas nozzle 115 to generate an O₂ gasplasma, and O₂ ⁺ etches the barrier metal film 123 on the surface of thesubstrate 103, thereby carrying out denitrification. Afterdenitrification, the amount of the O₂ gas is decreased to form the oxidelayer 124 (see FIG. 16).

[0514] In this case, the number of the nozzles for supplying the gasescan be decreased, thus bringing advantage in space.

[0515] The O₂ gas plasma can be used only for the formation of the oxidelayer 124 (see FIG. 16) without being used for etching. In this case,the barrier metal film 123 is only the single layer, MN layer 123 b. Ifthe metal to be formed as a film over the substrate 103 is a metalunproblematic in terms of adhesion (such as Al), for example, thetreatment for forming the metal layer 123 a by etching can be omitted.

[0516] Moreover, the O₂ gas plasma can be used similarly only for theformation of the oxide layer 124 (see FIG. 16) without being used foretching. After the MN layer 123 b is formed, the supply of the NH₃ gasand the supply of power to the power source 136 may be cut off. As aresult, the precursor (M_(x)Cl_(y)) 120 is transported toward thesubstrate 103 controlled to a lower temperature than the temperature ofthe metal member 107. The precursor (M_(x)Cl_(y)) 120 transported towardthe substrate 103 is converted into only metal (M) ions by a reductionreaction, and directed at the substrate 3. Thus, the metal layer 123 ais superposed on the MN layer 123 b of the substrate 103. In thismanner, the metal layer 123 a can be formed (see FIG. 21).

[0517] A barrier metal film production apparatus and a barrier metalfilm production method according to a twelfth embodiment of the presentinvention will be described with reference to FIGS. 23 to 25. FIG. 23 isa schematic side view of the barrier metal film production apparatusaccording to the twelfth embodiment of the present invention. FIG. 24 isa view taken along the arrowed line XIII-XIII of FIG. 23. FIG. 25 is aview taken along the arrowed line XIV-XIV of FIG. 24. The same membersas the members illustrated in FIGS. 12 to 22 are assigned the samenumerals, and duplicate explanations are omitted.

[0518] An upper surface of the chamber 101 is an opening, which isclosed with a disk-shaped ceiling board 141 made of an insulatingmaterial (for example, a ceramic). An etched member 142 made of a metal(e.g., W, Ti, Ta or TiSi) is interposed between the opening at the uppersurface of the chamber 101 and the ceiling board 141. The etched member142 is provided with a ring portion 143 fitted to the opening at theupper surface of the chamber 101. A plurality of (12 in the illustratedembodiment) protrusions 144, which extend close to the center in thediametrical direction of the chamber 101 and have the same width, areprovided in the circumferential direction on the inner periphery of thering portion 143.

[0519] The protrusions 144 are integrally or removably attached to thering portion 143. Notches (spaces) 145 formed between the protrusions144 are present between the ceiling board 141 and the interior of thechamber 101. The ring portion 143 is earthed, and the plural protrusions144 are electrically connected together and maintained at the samepotential. Temperature control means (not shown), such as a heater, isprovided in the etched member 142 to control the temperature of theetched member 142 to 200 to 400° C., for example.

[0520] Second protrusions shorter in the diametrical direction than theprotrusions 144 can be arranged between the protrusions 144. Moreover,short protrusions can be arranged between the protrusion 144 and thesecond protrusion. By so doing, the area of the etched member, an objectto be etched, can be secured, with an induced current being suppressed.

[0521] A planar winding-shaped plasma antenna 146, for converting theatmosphere inside the chamber 101 into a plasma, is provided above theceiling board 141. The plasma antenna 146 is formed in a planar ringshape parallel to the surface of the ceiling board 141. A matchinginstrument 110 and a power source 111 are connected to the plasmaantenna 146 to supply power. The etched member 142 has the plurality ofprotrusions 144 provided in the circumferential direction on the innerperiphery of the ring portion 143, and includes the notches (spaces) 145formed between the protrusions 144. Thus, the protrusions 144 arearranged between the substrate 103 and the ceiling board 141 in adiscontinuous state relative to the flowing direction of electricity inthe plasma antenna 146.

[0522] At a cylindrical portion of the chamber 101, there are provided anozzle 112 for supplying a source gas into the chamber 101, a nozzle 114for supplying an NH₃ gas into the chamber 101, a diluent gas nozzle 121for supplying an Ar gas into the chamber 101, an oxygen gas nozzle 115for supplying an O₂ gas into the chamber 101, and a hydrogen gas nozzle116 for supplying an H₂ gas into the chamber 101.

[0523] With the above-described barrier metal film production apparatus,the source gas is supplied through the nozzles 112 to the interior ofthe chamber 101, and electromagnetic waves are shot from the plasmaantenna 146 into the chamber 101. As a result, the Cl₂ gas is ionized togenerate a Cl₂ gas plasma (source gas plasma). The etched member 142, anelectric conductor, is present below the plasma antenna 146. However,the Cl₂ gas plasma occurs stably between the etched member 142 and thesubstrate 103, namely, below the etched member 142, under the followingaction:

[0524] The action by which the Cl₂ gas plasma is generated below theetched member 142 will be described. As shown in FIG. 25, a flow A ofelectricity in the plasma antenna 146 of the planar ring shape crossesthe protrusions 144. At this time, an induced current B occurs on thesurface of the protrusion 144 opposed to the plasma antenna 146. Sincethe notches (spaces) 145 are present in the etched member 142, theinduced current B flows onto the lower surface of each protrusion 144,forming a flow a in the same direction as the flow A of electricity inthe plasma antenna 146 (Faraday shield).

[0525] When the etched member 142 is viewed from the substrate 103,therefore, there is no flow in a direction in which the flow A ofelectricity in the plasma antenna 146 is canceled out. Furthermore, thering portion 143 is earthed, and the protrusions 144 are maintained atthe same potential. Thus, even though the etched member 142, an electricconductor, exists, the electromagnetic wave is reliably thrown from theplasma antenna 146 into the chamber 101. Consequently, the Cl₂ gasplasma is stably generated below the etched member 142.

[0526] The Cl₂ gas plasma causes an etching reaction to the etchedmember 142, forming a precursor (M_(x)Cl_(y): M is a metal such as W,Ti, Ta or TiSi) 120.

[0527] Separately, the NH₃ gas is supplied into the chamber 101 throughthe nozzle 114, and electromagnetic waves are shot from the plasmaantenna 146 into the chamber 110. Thus, the NH₃ gas is ionized togenerate an NH₃ gas plasma, which causes a reduction reaction with theprecursor 120, forming a metal nitride (MN). The metal nitride (MN)formed within the chamber 101 is transported toward the substrate 103controlled to a low temperature, whereupon MN is formed into a film onthe surface of the substrate 103 to produce a barrier metal film 123(see FIG. 13).

[0528] After the barrier metal film 123 has been formed, the Ar gas issupplied from the diluent gas nozzle 121, and electromagnetic waves areshot from the plasma antenna 146 into the chamber 101, therebygenerating an Ar gas plasma. Generation of the Ar gas plasma results inthe etching of the barrier metal film 123 on the surface of thesubstrate 103, thereby performing denitrification, a treatment forremoving the nitrogen atoms (N) of the MN in the superficial layer ofthe barrier metal film 123 to decrease the nitrogen content of thesuperficial layer relative to the interior of the matrix of the barriermetal film 123.

[0529] Immediately before formation of the most superficial layer of thebarrier metal film 123 is completed, a trace amount of O₂ gas issupplied through the oxygen gas nozzle 115 into the chamber 101. At thesame time, electromagnetic waves are shot from the plasma antenna 146into the chamber 101 to generate an O₂ gas plasma. As a result, an oxidelayer 124 (see FIG. 16) is formed on the surface of the metal layer 123a composed substantially of M (see FIG. 16). Since the oxide layer 124has been formed, if a metal (e.g., copper) is deposited (formed as afilm) on the surface of the barrier metal film 123, wetting with themetal is satisfactory, thus increasing adhesion.

[0530] After formation of the oxide layer 124 (see FIG. 16) on thesurface of the metal layer 123 a (FIG. 16), the H₂ gas is supplied fromthe hydrogen gas nozzle 116 into the chamber 101, and electromagneticwaves are shot from the plasma antenna 146 into the chamber 101, therebygenerating an H₂ gas plasma. As a result, hydroxyl groups (OH groups)are formed on the surface of the oxide layer 124 (see FIG. 18). Thesehydroxyl groups increase hydrophilicity, and can further enhance theadhesion of the metal (copper) to be formed as a film.

[0531] It is permissible to omit the step of generating the H₂ gasplasma to form hydroxyl groups (OH groups) on the surface of the oxidelayer 124 (see FIG. 18). It is also allowable to omit the step ofgenerating the O₂ gas plasma to form the oxide layer 124 (FIG. 16) onthe surface of the metal layer 123 a (FIG. 16). Furthermore, it ispossible to superpose the metal layer 123 a, forming the barrier metalfilm 123. It is also possible to form the barrier metal film 123 freefrom the metal layer 123 a.

[0532] Beside, the same nozzle construction as in the tenth embodiment(see FIG. 20) omitting the diluent gas nozzle 121 may be adopted in aconfiguration for formation of the precursor 120 with the exception ofthe etched member 142 and the plasma antenna 146. Moreover, the sameconstruction as in the eleventh embodiment (see FIG. 22) having theexcitation chamber 133, etc. instead of the nozzle 114 may be adopted ina configuration excepting the etched member 142 and the plasma antenna146.

[0533] With the above-described barrier metal film production apparatus,the barrier metal film 123 can be formed uniformly to a small thickness.Consequently, the barrier metal film 123 can be formed highly accuratelyat a high speed with excellent burial properties in a very smallthickness even to the interior of a tiny depression, for example severalhundred nanometers wide, which has been provided in the substrate 103.

[0534] In addition, the etched member 142 has the plurality ofprotrusions 144 provided in the circumferential direction on the innerperiphery of the ring portion 143, and includes the notches (spaces) 145formed between the protrusions 144. Thus, the induced currents generatedin the etched member 142 flow in the same direction as the flowingdirection of electricity in the plasma antenna 146, when viewed from thesubstrate 103. Therefore, even though the etched member 142, an electricconductor, exists below the plasma antenna 146, the electromagneticwaves are reliably thrown from the plasma antenna 146 into the chamber101. Consequently, the Cl₂ gas plasma can be stably generated below theetched member 142.

[0535] A barrier metal film production apparatus and a barrier metalfilm production method according to the thirteenth embodiment of thepresent invention will be described with reference to FIG. 26. FIG. 26is a schematic side view of a barrier metal film production apparatusaccording to the third embodiment of the present invention. The samemembers as the members illustrated in FIGS. 12 to 25 are assigned thesame numerals, and duplicate explanations are omitted.

[0536] The opening of an upper portion of a chamber 101 is closed with aceiling board 141. An etched member 148 made of a metal (e.g., W, Ti, Taor TiSi) is provided on a lower surface of the ceiling board 141, andthe etched member 148 is of a quadrangular pyramidal shape. Slit-shapedopening portions 151 are formed at a plurality of locations (forexample, four locations; one of the locations is shown in the drawing)in the periphery of an upper part of the cylindrical portion of thechamber 101, and one end of a tubular passage 152 is fixed to theopening portion 151. A tubular excitation chamber 153 made of aninsulator is provided halfway through the passage 152, and a coiledplasma antenna 154 is provided around the excitation chamber 153. Theplasma antenna 154 is connected to a matching instrument 157 and a powersource 158 to receive power.

[0537] A flow controller 155 is connected to the other end of thepassage 152, and a chlorine-containing source gas (a Cl₂ gas dilutedwith He or Ar to a chlorine concentration of ≦ 50%, preferably about10%) is supplied into the passage 152 via the flow controller 155. Byshooting electromagnetic waves from the plasma antenna 154 into theexcitation chamber 153, the Cl₂ gas is ionized to generate a Cl₂ gasplasma (source gas plasma) 156. Because of the generation of the Cl₂ gasplasma 156, excited chlorine is fed into the chamber 101 through theopening portion 151, whereupon the etched member 148 is etched withexcited chlorine.

[0538] At a cylindrical portion of the chamber 101, there are provided anozzle 114 for supplying an NH₃ gas into the chamber 101, a diluent gasnozzle 121 for supplying an Ar gas into the chamber 101, an oxygen gasnozzle 115 for supplying an O₂ gas into the chamber 101, and a hydrogengas nozzle 116 for supplying an H₂ gas into the chamber 101. Around thechamber 101, a plasma antenna 109, a matching instrument 110 and a powersource 111 are provided to generate an NH₃ gas plasma, an Ar gas plasma,an O₂ gas plasma, and an H₂ gas plasma.

[0539] With the above-described barrier metal film production apparatus,the source gas is supplied into the passage 152 via the flow controller155 and fed into the excitation chamber 153. By shooting electromagneticwaves from the plasma antenna 154 into the excitation chamber 153, theCl₂ gas is ionized to generate a Cl₂ gas plasma (source gas plasma) 156.Since a predetermined differential pressure has been established betweenthe pressure inside the chamber 101 and the pressure inside theexcitation chamber 153 by the vacuum device 108, the excited chlorine ofthe Cl₂ gas plasma 156 in the excitation chamber 153 is fed to theetched member 148 inside the chamber 101 through the opening portion151. The excited chlorine causes an etching reaction to the etchedmember 148, forming a precursor 120 inside the chamber 101. At thistime, the etched member 148 is maintained at a predetermined temperature(e.g., 200 to 400° C.), which is higher than the temperature of thesubstrate 103, by a heater 150 provided in the ceiling board 141.

[0540] Separately, the NH₃ gas is supplied into the chamber 101 throughthe nozzle 114, and electromagnetic waves were shot from the plasmaantenna 109 into the chamber 101. Thus, the NH₃ gas is ionized togenerate an NH₃ gas plasma, which causes a reduction reaction with theprecursor 120, forming a metal nitride (MN). The metal nitride (MN)formed within the chamber 101 is transported toward the substrate 103controlled to a low temperature, whereupon MN is formed into a film onthe surface of the substrate 103 to produce a barrier metal film 123(see FIG. 13).

[0541] After the barrier metal film 123 has been formed, the Ar gas issupplied from the diluent gas nozzle 121, and electromagnetic waves areshot from the plasma antenna 109 into the chamber 101, therebygenerating an Ar gas plasma. Generation of the Ar gas plasma results inthe etching of the barrier metal film 123 on the surface of thesubstrate 103, thereby performing denitrification, a treatment forremoving the nitrogen atoms (N) of the MN in the superficial layer ofthe barrier metal film 123 to decrease the nitrogen content of thesuperficial layer relative to the interior of the matrix of the barriermetal film 123.

[0542] Immediately before formation of the most superficial layer of thebarrier metal film 123 is completed, a trace amount of O₂ gas issupplied through the oxygen gas nozzle 115 into the chamber 101. At thesame time, electromagnetic waves are shot from the plasma antenna 109into the chamber 101 to generate an O₂ gas plasma. As a result, an oxidelayer 124 (see FIG. 16) is formed on the surface of the metal layer 123a composed substantially of M (see FIG. 16). Since the oxide layer 124has been formed, if a metal (e.g., copper) is deposited (formed as afilm) on the surface of the barrier metal film 123, wetting with themetal is satisfactory, thus increasing adhesion.

[0543] After formation of the oxide layer 124 (see FIG. 16) on thesurface of the metal layer 123 a (FIG. 16), the H₂ gas is supplied fromthe hydrogen gas nozzle 116 into the chamber 101, and electromagneticwaves are shot from the plasma antenna 109 into the chamber 101, therebygenerating an H₂ gas plasma. As a result, hydroxyl groups (OH groups)are formed on the surface of the oxide layer 124 (see FIG. 18). Thesehydroxyl groups increase hydrophilicity, and can further enhance theadhesion of the metal (copper) to be formed as a film.

[0544] It is permissible to omit the step of generating the H₂ gasplasma to form hydroxyl groups (OH groups) on the surface of the oxidelayer 124 (see FIG. 18). It is also allowable to omit the step ofgenerating the O₂ gas plasma to form the oxide layer 124 (FIG. 16) onthe surface of the metal layer 123 a (FIG. 16). Furthermore, it ispossible to superpose the metal layer 123 a, forming the barrier metalfilm 123. It is also possible to form the barrier metal film 123 freefrom the metal layer 123 a.

[0545] Beside, the same nozzle construction as in the tenth embodiment(see FIG. 20) omitting the diluent gas nozzle 121 may be adopted in aconfiguration for formation of the precursor 120 with the exception ofthe etched member 148, opening portion 151, passage 152, excitationchamber 153, plasma antenna 154, flow controller 155, matchinginstrument 157, and power source 158. Moreover, the same construction asin the eleventh embodiment (see FIG. 22) having the excitation chamber133, etc. instead of the nozzle 114 may be adopted in otherconfiguration for formation of the precursor 120.

[0546] With the above-described barrier metal film production apparatus,the barrier metal film 123 can be formed uniformly to a small thickness.Consequently, the barrier metal film 123 can be formed highly accuratelyat a high speed with excellent burial properties in a very smallthickness even to the interior of a tiny depression, for example severalhundred nanometers wide, which has been provided in the substrate 103.

[0547] Furthermore, the Cl₂ gas plasma 156 is generated in theexcitation chamber 153 isolated from the chamber 101. Thus, thesubstrate 103 is not exposed to the Cl₂ gas plasma 156 any more, and thesubstrate 103 becomes free from damage from the Cl₂ gas plasma 156.

[0548] As the means for generating the Cl₂ gas plasma 156 in theexcitation chamber 153, namely, the means for exciting the source gas toconvert it into an excited source gas, it is possible to use microwaves,laser, electron rays, or synchrotron radiation. It is also permissibleto form the precursor by heating the metal filament to a hightemperature. The construction for isolating the Cl₂ gas plasma 156 fromthe substrate 103 may be the provision of the excitation chamber 153 inthe passage 152, or may be other construction, for example, theisolation of the chamber 101.

[0549] A barrier metal film production apparatus and a barrier metalfilm production method according to the fourteenth embodiment of thepresent invention will be described with reference to FIG. 27. FIG. 27is a schematic side view of the barrier metal film production apparatusaccording to the fourteenth embodiment of the present invention. Thesame members as the members illustrated in FIGS. 12 to 26 are assignedthe same numerals, and duplicate explanations are omitted.

[0550] In the barrier metal film production apparatus according to thefourteenth embodiment, unlike the barrier metal film productionapparatus according to the ninth embodiment shown in FIG. 12, the plasmaantenna 9 is not provided around the cylindrical portion of the chamber101, but a metal member 107 is connected to a matching instrument 110and a power source 111 to receive power.

[0551] At the cylindrical portion of the chamber 101, there are provideda nozzle 114 for supplying an NH₃ gas into the chamber 101, a diluentgas nozzle 121 for supplying an Ar gas into the chamber 101, an oxygengas nozzle 115 for supplying an O₂ gas into the chamber 101, and ahydrogen gas nozzle 116 for supplying an H₂ gas into the chamber 101. Bysupplying power to the metal member 107, an NH₃ gas plasma, an Ar gasplasma, an O₂ gas plasma, and an H₂ gas plasma are generated. Togenerate the NH₃ gas plasma, Ar gas plasma, O₂ gas plasma, and H₂ gasplasma, a coiled plasma antenna may be provided separately on thecylindrical portion of the chamber 101, and the plasma antenna may beconnected to a power source via a matching instrument.

[0552] With the above-described barrier metal film production apparatus,the source gas is supplied from the nozzle 112 into the chamber 101, andelectromagnetic waves are shot from the metal member 107 into thechamber 101, whereby the Cl₂ gas is ionized to generate a Cl₂ gas plasma(source gas plasma). The Cl₂ gas plasma causes an etching reaction tothe metal member 107, producing a precursor (M_(x)Cl_(y)) 120. At thistime, the metal member 107 is maintained at a predetermined temperature(e.g., 200 to 400° C., which is higher than the temperature of thesubstrate 103, by temperature control means (not shown).

[0553] Separately, the NH₃ gas is supplied into the chamber 101 throughthe nozzle 114, and electromagnetic waves are shot from the metal member107 into the chamber 101. Thus, the NH₃ gas is ionized to generate anNH₃ gas plasma, which causes a reduction reaction with the precursor120, forming a metal nitride (MN). The metal nitride (MN) formed withinthe chamber 101 is transported toward the substrate 103 controlled to alow temperature, whereupon MN is formed into a film on the surface ofthe substrate 103 to produce a barrier metal film 123 (see FIG. 13).

[0554] After the barrier metal film 123 has been formed, the Ar gas issupplied from the diluent gas nozzle 121, and electromagnetic waves areshot from the metal member 107 into the chamber 101, thereby generatingan Ar gas plasma. Generation of the Ar gas plasma results in the etchingof the barrier metal film 123 on the surface of the substrate 103,thereby performing denitrification, a treatment for removing thenitrogen atoms (N) of the MN in the superficial layer of the barriermetal film 123 to decrease the nitrogen content of the superficial layerrelative to the interior of the matrix of the barrier metal film 123.

[0555] Immediately before formation of the most superficial layer of thebarrier metal film 123 is completed, a trace amount of O₂ gas issupplied through the oxygen gas nozzle 115 into the chamber 101. At thesame time, electromagnetic waves are shot from the metal member 107 intothe chamber 101 to generate an O₂ gas plasma. As a result, an oxidelayer 124 (see FIG. 16) is formed on the surface of a metal layer 123 acomposed substantially of M (see FIG. 16). Since the oxide layer 124 hasbeen formed, if a metal (e.g., copper) is deposited (formed as a film)on the surface of the barrier metal film 123, wetting with the metal issatisfactory, thus increasing adhesion.

[0556] After formation of the oxide layer 124 (see FIG. 16) on thesurface of the metal layer 123 a (FIG. 16), the H₂ gas is supplied fromthe hydrogen gas nozzle 116 into the chamber 101, and electromagneticwaves are shot from the metal member 107 into the chamber 101, therebygenerating an H₂ gas plasma. As a result, hydroxyl groups (OH groups)are formed on the surface of the oxide layer 124 (see FIG. 18). Thesehydroxyl groups increase hydrophilicity, and can further enhance theadhesion of the metal (copper) to be formed as a film.

[0557] It is permissible to omit the step of generating the H₂ gasplasma to form hydroxyl groups (OH groups) on the surface of the oxidelayer 124 (see FIG. 18). It is also allowable to omit the step ofgenerating the O₂ gas plasma to form the oxide layer 124 (FIG. 16) onthe surface of the metal layer 123 a (FIG. 16). Furthermore, it ispossible to superpose the metal layer 123 a, forming the barrier metalfilm 123. It is also possible to form the barrier metal film 123 freefrom the metal layer 123 a.

[0558] Beside, the same nozzle construction as in the tenth embodiment(see FIG. 20) omitting the diluent gas nozzle 121 may be adopted in theconfiguration for formation of the precursor 120 with the exception ofthe metal member 107, matching instrument 110, and power source 111.Moreover, the same construction as in the eleventh embodiment (see FIG.22) having the excitation chamber 133, etc. instead of the nozzle 114may be adopted in other configuration for formation of the precursor120.

[0559] With the above-described barrier metal film production apparatus,the barrier metal film 123 can be formed uniformly to a small thickness.Consequently, the barrier metal film 123 can be formed highly accuratelyat a high speed with excellent burial properties in a very smallthickness even to the interior of a tiny depression, for example severalhundred nanometers wide, which has been provided in the substrate 103.

[0560] Furthermore, the metal member 107 itself is applied as anelectrode for plasma generation. Thus, there is no need for a plasmaantenna around the cylindrical portion of the chamber 101, and thedegree of freedom of the surrounding construction can be increased.

[0561] A metal film production method and a metal film productionapparatus according to the present invention will be described withreference to the accompanying drawings. The metal film production methodof the present invention involves a treatment for enhancing adhesion toa barrier metal layer of, for example, tantalum nitride (TaN) formed onthe surface of a substrate in order to prevent diffusion into thesubstrate.

[0562] According to a first aspect of the present invention, the barriermetal film of TaN is flattened by etching its surface with a diluent gas(e.g., argon: Ar) plasma. Further, the nitrogen atoms in the superficiallayer of the barrier metal film are removed using Ar⁺, therebydecreasing the nitrogen content of the superficial layer relative to theinterior of the matrix of the barrier metal film (this surface treatmentwill be referred to hereinafter as denitrification). The denitrificationbrings a state in which a film of a metal (Ta) is substantially formedin the superficial layer of the single-layer barrier metal film. In thismanner, a barrier metal film is produced highly efficiently and reliablyin a thin film condition, by use of an inexpensive gas having a highmass number, with the diffusion of the metal being prevented and theadhesion to the metal being maintained.

[0563] Depending on the material for the barrier metal film, it ispossible to perform only the treatment for flattening the surface byetching it with the diluent gas (e.g., argon: Ar) plasma whilecontrolling the power of the plasma and the energization time. By sodoing, adhesion can be improved. As the barrier metal film, not onlyTaN, but tungsten nitride or titanium nitride can be applied. As thediluent gas, not only Ar, but helium, krypton, or neon can be applied.

[0564] The concrete construction of the apparatus according to the firstaspect may be as follows: A source gas containing a halogen (e.g., achlorine-containing gas) is supplied to the interior of a chamberbetween a substrate and an etched member made of Ta, and an atmospherewithin the chamber is converted into a plasma to generate a chlorine gasplasma. The etched member is etched with the chlorine gas plasma to forma precursor comprising the Ta component contained in the etched memberand the chlorine gas. Also, a nitrogen-containing gas is excited, andTaN, a metal nitride, is formed upon reaction between the excitednitrogen and the precursor. The resulting TaN is formed as a film on thesubstrate kept at a low temperature to form a barrier metal film. Thisprocess is performed using a barrier metal film production apparatus.After the barrier metal film is produced in this manner, an Ar gasplasma is generated within the chamber to carry out etching anddenitrification.

[0565] Alternatively, the concrete apparatus construction of the firstaspect may be as follows: A chlorine gas is supplied into a chamber, andan atmosphere within the chamber is converted into a plasma to generatea chlorine gas plasma. An etched member made of copper (Cu) is etchedwith the chlorine gas plasma to form a precursor comprising the Cucomponent contained in the etched member and chlorine inside thechamber. The temperature of the substrate is rendered lower than thetemperature of the etched member to form a film of the Cu component ofthe precursor on the substrate. This process is performed by use of ametal film production apparatus. Before the substrate having the barriermetal film of TaN formed thereon is housed in the chamber and the Cucomponent is formed as a film thereon, the Ar gas plasma is generated tocarry out etching and denitrification.

[0566]FIG. 28 shows an outline of an apparatus for a film formationprocess for forming a Cu film. As shown, for example, in FIG. 28, ahandling robot 401 for transporting a substrate is installed at acentral site. Around the robot 401, there are provided an accommodationdevice 402 for accommodating the substrate, a barrier metal CVD 403 forforming a barrier metal film on the substrate, and a Cu-CVD 404 forforming a Cu film. The robot 401 transports the substrate from theaccommodation device 402 to the barrier metal CVD 403, from the barriermetal CVD 403 to the Cu-CVD 404, and from the Cu-CVD 404 to theaccommodation device 402. With such an apparatus for the film formationprocess, the metal film production apparatus according to the firstaspect is provided in the Cu-CVD 404.

[0567] The metal film production apparatus in the first aspect may beprovided in the barrier metal CVD 403, or a dedicated metal filmproduction apparatus according to the first aspect may be providedaround the robot 401.

[0568] Embodiments of the metal film production method and metal filmproduction apparatus according to the first aspect will be describedwith reference to the accompanying drawings, with the provision of theapparatus in the Cu-CVD 404 being taken as an example.

[0569]FIG. 29 is a schematic side view of a metal film productionapparatus according to the fifteenth embodiment of the presentinvention. FIG. 30 is a schematic construction drawing showing anotherexample of diluent gas supply means. FIG. 31 shows the sectional statusof a substrate illustrating a barrier metal film. FIGS. 32 and 33 showthe concept status of a barrier metal film in denitrification. Theillustrated metal film production apparatus corresponds to the Cu-CVD404 shown in FIG. 1.

[0570] As shown in FIG. 29, a support platform 202 is provided near thebottom of a cylindrical chamber 201 made of, say, a ceramic (aninsulating material), and a substrate 203 is placed on the supportplatform 202. Temperature control means 206, as control means, equippedwith a heater 204 and refrigerant flow-through means 205 is provided inthe support platform 202 so that the support platform 202 is controlledto a predetermined temperature (for example, a temperature at which thesubstrate 203 is maintained at 100 to 200° C.) by the temperaturecontrol means 206.

[0571] An upper surface of the chamber 201 is an opening, which isclosed with a copper plate member 207, as an etched member, made of ametal. The interior of the chamber 201 closed with the copper platemember 207 is maintained at a predetermined pressure by a vacuum device208. A coiled plasma antenna 209 is provided around a cylindricalportion of the chamber 201. A matching instrument 210 and a power source211 are connected to the plasma antenna 209 to supply power. Plasmageneration means is constituted by the plasma antenna 209, matchinginstrument 210 and power source 211.

[0572] Nozzles 212 for supplying a source gas (a Cl₂ gas diluted with Heor Ar to a chlorine concentration of ≦50%, preferably about 10%),containing chlorine as a halogen, to the interior of the chamber 201 areconnected to the cylindrical portion of the chamber 201 above thesupport platform 202. The nozzle 212 is fed with the source gas via aflow controller 213. Within the chamber 201, the source gas is fedtoward the copper plate member 207 (source gas supply means). Fluorine(F), bromine (Br) or iodine (I) can also be applied as the halogen to beincorporated into the source gas.

[0573] With the above-described metal film production apparatus, thesource gas is supplied from the nozzles 212 into the chamber 201, andelectromagnetic waves are shot from the plasma antenna 209 into thechamber 201, whereby the Cl₂ gas is ionized to generate a Cl₂ gas plasma(source gas plasma) 214. The pressure inside the chamber 201, set by thevacuum device 208, is such a high pressure that the plasma density ofthe Cl₂ gas plasma 214 will be higher toward the wall surface within thechamber 201. As means for increasing the plasma density of the Cl₂ gasplasma 214 on the wall surface side, the frequency of the power source211 may be increased.

[0574] The Cl₂ gas plasma 214 causes an etching reaction to the copperplate member 207, forming a precursor (Cu_(x)Cl_(y)) 215. At this time,the copper plate member 207 is maintained by the Cl₂ gas plasma 214 at apredetermined temperature (e.g., 200 to 400° C.) which is higher thanthe temperature of the substrate 203.

[0575] The precursor (Cu_(x)Cl_(y)) 215 formed within the chamber 201 istransported toward the substrate 203 controlled to a lower temperaturethan the temperature of the copper plate member 207. The precursor(Cu_(x)Cl_(y)) 215 transported toward the substrate 203 is convertedinto only Cu ions by a reduction reaction, and directed at the substrate203 to form a thin Cu film 216 on the surface of the substrate 203.

[0576] The reactions involved can be expressed by:

2Cu+Cl₂→2CuCl→2Cu↓+Cl₂↑

[0577] The gases and the etching products that have not been involved inthe reaction are exhausted through an exhaust port 217.

[0578] The source gas has been described, with the Cl₂ gas diluted with,say, He or Ar taken as an example. However, the Cl₂ gas can be usedalone, or an HCl gas can also be applied. If the HCl gas is applied, anHCl gas plasma is generated as the source gas plasma. However, theprecursor formed by etching of the copper plate member 207 isCu_(x)Cl_(y). Thus, the source gas may be any gas containing chlorine,and a gas mixture of an HCl gas and a Cl₂ gas is also usable. Thematerial for the copper plate member 207 is not limited to copper (Cu),but it is possible to use a halide forming metal, preferably a chlorideforming metal, such as Ag, Au, Pt, Ta, Ti or W. In this case, theresulting precursor is a halide (chloride) of Ag, Au, Pt, Ta, Ti or W,and the thin film formed on the surface of the substrate 203 is that ofAg, Au, Pt, Ta, Ti or W.

[0579] Since the metal film production apparatus constructed as aboveuses the Cl₂ gas plasma (source gas plasma) 214, the reaction efficiencyis markedly increased, and the speed of film formation is fast. Sincethe Cl₂ gas is used as the source gas, moreover, the cost can bemarkedly decreased. Furthermore, the substrate 203 is controlled to alower temperature than the temperature of the copper plate member 207 byuse of the temperature control means 206. Thus, the amounts ofimpurities, such as chlorine, remaining in the thin Cu film 216 can bedecreased, so that a high quality thin Cu film 216 can be produced.

[0580] Furthermore, the plasma density of the Cl₂ gas plasma 214 ishigher on the wall surface side. Thus, a high density Cl₂ gas plasma 214can be generated, thus making the film formation speed remarkably high.Even when a large chamber 201 is used, namely, even for a largesubstrate 203, a thin Cu film 216 can be formed.

[0581] Diluent gas nozzles 221 are provided, as diluent gas supplymeans, for supplying an Ar gas, as a diluent gas, to the interior of thechamber 201 above the surface of the substrate 203. The Ar gas issupplied from the diluent gas nozzle 221, and electromagnetic waves areshot from the plasma antenna 209 into the chamber 201, whereby the Argas is ionized to generate an Ar gas plasma (surface treatment plasmageneration means). A bias power source 220 is connected to the supportplatform 202, and a bias voltage is applied thereto for supporting thesubstrate 203 on the support platform 202.

[0582] In connection with the diluent gas supply means, when the Ar gasis applied as a diluent gas for the Cl₂ gas, a control valve 222 may beprovided at the site of merger between the source gas (Cl₂ gas) and thediluent gas (Ar gas), as shown in FIG. 30. By so doing, the Cl₂ gas maybe stopped during generation of the Ar gas plasma, and only the Ar gasmay be supplied through the nozzle 212. According to this construction,there is no need for the provision of the diluent gas nozzle 221,presenting advantage in space.

[0583] On the surface of the substrate 203 carried into theabove-described metal film production apparatus, the barrier metal film223 of TaN has been formed, as shown in FIG. 31. By generating the Argas plasma, the barrier metal film 223 on the surface of the substrate203 is etched with Ar⁺ to flatten the barrier metal film 223. Also,denitrification is performed in which the nitrogen atoms (N) of the TaNin the superficial layer of the barrier metal film 223 are removed todecrease the nitrogen content of the superficial layer relative to theinterior of the matrix of the barrier metal film 223. As the barriermetal film 223, WN or TiN can also be applied.

[0584] The flattening of the barrier metal film 223 and itsdenitrification upon generation of the Ar gas plasma are carried outbefore formation of the aforementioned thin Cu film 216. That is, whenthe substrate 203 having the barrier metal film 223 of TaN formedthereon is received onto the support platform 202, the Ar gas issupplied from the diluent gas nozzles 221 prior to the formation of thethin Cu film 216. At the same time, electromagnetic waves are shot fromthe plasma antenna 209 into the chamber 201 to generate an Ar gasplasma.

[0585] Upon generation of the Ar gas plasma, the surface of the barriermetal film 223 is etched with Ar⁺ for flattening. As shown in FIG. 32,the barrier metal film 223 comprises Ta and N in an amorphous state. Inthis state, N of a lower mass is preferentially removed by Ar⁺, so thatthe superficial layer of the barrier metal film 223 (for example, up toa half, preferably about a third, of the entire film thickness) isdenitrified. As a result, there emerges the barrier metal film 223 of atwo-layer structure, a metal layer 223 a substantially composed of Ta,and a TaN layer 223 b, as shown in FIG. 33. On this occasion, the entirefilm thickness of the barrier metal film 223 remains the film thicknesshaving the single layer.

[0586] To increase the amount of Ar⁺ generated, control is exercised forincreasing the voltage applied to the plasma antenna 209, or forincreasing the flow rate of the Ar gas. To draw in Ar⁺ toward thesubstrate 203, the bias power source 220 is controlled to lower thepotential of the substrate 203 to the negative side. For this purpose,schedule control is easy to effect according to a preset schedule. Whiledenitrification is taking place, the depth distribution of the metallayer 223 a is measured. Control over the voltage of the plasma antenna209 or the flow rate of the Ar gas, or control of the bias power source220 can be exercised based on the results of the measurement.

[0587] After denitrification is performed, the sites of N removed becomevoids, creating irregularities on the atomic level. Thus, it ispreferred to densify the remaining Ta atoms. To make the Ta atoms dense,the present embodiment uses a heater 204 to heat the substrate 203 forheat treatment, thereby densifying the Ta atoms (densification means).The heat treatment is performed to such a degree that the atoms do nottake a crystal structure (the atoms maintain an amorphous state). Thedensification means may be plasma heating for heating the substrate 203.

[0588] With the foregoing metal film production apparatus, the Ar gasplasma is generated within the chamber 201 accommodating the substrate203 having the barrier metal film 223 formed thereon. The Ar gas plasmaetches the barrier metal film 223 to flatten it. The Ar gas plasma alsoremoves the nitrogen atoms to denitrify the barrier metal film 223.Thus, there appears the barrier metal film 223 with a two-layerstructure, i.e., the metal layer 223 a composed substantially of Ta andthe TaN layer 223 b. Moreover, the entire film thickness can remain thesingle-layer film thickness. Hence, the barrier metal film 223 can be ina two-layer structure state without becoming thick, and yet the metallayer 223 a can retain adhesion to the thin Cu film 216, while the TaNlayer 223 b can prevent diffusion of Cu. Consequently, the thin Cu film216 can be formed, with satisfactory adhesion, without diffusion intothe substrate 203, so that the Cu wiring process can be stabilized.

[0589] A barrier metal film production method and a barrier metal filmproduction apparatus according to the sixteenth embodiment of thepresent invention will be described with reference to FIGS. 34 to 36.FIG. 34 is a schematic side view of the metal film production apparatusaccording to the sixteenth embodiment of the present invention. FIG. 35is a view taken along the arrowed line VIII-VIII of FIG. 34. FIG. 36 isa view taken along the arrowed line IX-IX of FIG. 35. The same membersas the members illustrated in FIG. 29 are assigned the same numerals,and duplicate explanations are omitted.

[0590] An upper surface of the chamber 201 is an opening, which isclosed with a disk-shaped ceiling board 230 made of an insulatingmaterial (for example, a ceramic). An etched member 231 made of a metal(copper, Cu) is interposed between the opening at the upper surface ofthe chamber 201 and the ceiling board 230. The etched member 231 isprovided with a ring portion 232 fitted to the opening at the uppersurface of the chamber 201. A plurality of (12 in the illustratedembodiment) protrusions 233, which extend close to the center in thediametrical direction of the chamber 201 and have the same width, areprovided in the circumferential direction on the inner periphery of thering portion 232.

[0591] The protrusions 233 are integrally or removably attached to thering portion 232. Notches (spaces) 235 formed between the protrusions233 are present between the ceiling board 230 and the interior of thechamber 201. The ring portion 232 is earthed, and the plural protrusions233 are electrically connected together and maintained at the samepotential. Temperature control means (not shown), such as a heater, isprovided in the etched member 231 to control the temperature of theetched member 231 to 200 to 400° C., for example.

[0592] Second protrusions shorter in the diametrical direction than theprotrusions 233 can be arranged between the protrusions 233. Moreover,short protrusions can be arranged between the protrusion 233 and thesecond protrusion. By so doing, the area of copper, an object to beetched, can be secured, with an induced current being suppressed.

[0593] A planar winding-shaped plasma antenna 234, for converting theatmosphere inside the chamber 201 into a plasma, is provided above theceiling board 230. The plasma antenna 234 is formed in a planar ringshape parallel to the surface of the ceiling board 230. A matchinginstrument 210 and a power source 211 are connected to the plasmaantenna 234 to supply power. The etched member 231 has the plurality ofprotrusions 233 provided in the circumferential direction on the innerperiphery of the ring portion 232, and includes the notches (spaces) 235formed between the protrusions 233. Thus, the protrusions 233 arearranged between the substrate 203 and the ceiling board 230 in adiscontinuous state relative to the flowing direction of electricity inthe plasma antenna 234.

[0594] With the above-described metal film production apparatus, thesource gas is supplied through the nozzles 212 to the interior of thechamber 201, and electromagnetic waves are shot from the plasma antenna234 into the chamber 201. As a result, the Cl₂ gas is ionized togenerate a Cl₂ gas plasma (source gas plasma) 214. The etched member231, an electric conductor, is present below the plasma antenna 234.However, the Cl₂ gas plasma 214 occurs stably between the etched member231 and the substrate 203, namely, below the etched member 231, underthe following action:

[0595] The action by which the Cl₂ gas plasma 214 is generated below theetched member 231 will be described. As shown in FIG. 36, a flow A ofelectricity in the plasma antenna 234 of the planar ring shape crossesthe protrusions 233. At this time, an induced current B occurs on thesurface of the protrusion 233 opposed to the plasma antenna 234. Sincethe notches (spaces) 235 are present in the etched member 231, theinduced current B flows onto the lower surface of each protrusion 233,forming a flow a in the same direction as the flow A of electricity inthe plasma antenna 234 (Faraday shield).

[0596] When the etched member 231 is viewed from the substrate 203,therefore, there is no flow in a direction in which the flow A ofelectricity in the plasma antenna 234 is canceled out. Furthermore, thering portion 232 is earthed, and the protrusions 233 are maintained atthe same potential. Thus, even though the etched member 231, an electricconductor, exists, the electromagnetic wave is reliably thrown from theplasma antenna 234 into the chamber 201. Consequently, the Cl₂ gasplasma 214 is stably generated below the etched member 231.

[0597] The Cl₂ gas plasma 214 causes an etching reaction to the etchedmember 231 made of copper, forming a precursor (Cu_(x)Cl_(y)) 215. Atthis time, the etched member 231 is maintained by the Cl₂ gas plasma 214at a predetermined temperature (e.g., 200 to 400° C.) which is higherthan the temperature of the substrate 203. The precursor (Cu_(x)Cl_(y))215 formed within the chamber 201 is transported toward the substrate203 controlled to a lower temperature than the temperature of the etchedmember 231. The precursor (Cu_(x)Cl_(y)) 215 transported toward thesubstrate 203 is converted into only Cu ions by a reduction reaction,and directed at the substrate 203 to form a thin Cu film 216 on thesurface of the substrate 203.

[0598] The reactions involved are the same as in the aforementionedfifteenth embodiment. The gases and the etching products, which have notbeen involved in the reactions, are exhausted through an exhaust port217.

[0599] Since the metal film production apparatus constructed as aboveuses the Cl₂ gas plasma (source gas plasma) 214, the reaction efficiencyis markedly increased, and the speed of film formation is fast. Sincethe Cl₂ gas is used as the source gas, moreover, the cost can bemarkedly decreased. Furthermore, the substrate 203 is controlled to alower temperature than the temperature of the etched member 231 by useof the temperature control means 206. Thus, the amounts of impurities,such as chlorine, remaining in the thin Cu film 216 can be decreased, sothat a high quality thin Cu film 216 can be produced.

[0600] In addition, the etched member 231 has the plurality ofprotrusions 233 provided in the circumferential direction on the innerperiphery of the ring portion 232, and includes the notches (spaces) 235formed between the protrusions 233. Thus, the induced currents generatedin the etched member 231 flow in the same direction as the flowingdirection of electricity in the plasma antenna 234, when viewed from thesubstrate 203. Therefore, even though the etched member 231, an electricconductor, exists below the plasma antenna 234, the electromagneticwaves are reliably thrown from the plasma antenna 234 into the chamber201. Consequently, the Cl₂ gas plasma 214 can be stably generated belowthe etched member 231.

[0601] Diluent gas nozzles 221 are provided, as diluent gas supplymeans, for supplying an Ar gas, as a diluent gas, to the interior of thechamber 201 above the surface of the substrate 203. The Ar gas issupplied from the diluent gas nozzle 221, and electromagnetic waves areshot from the plasma antenna 234 into the chamber 201, whereby the Argas is ionized to generate an Ar gas plasma (surface treatment plasmageneration means). A bias power source 220 is connected to the supportplatform 202, and a bias voltage is applied thereto for supporting thesubstrate 203 on the support platform 202.

[0602] On the surface of the substrate 203 admitted into theabove-described metal film production apparatus, the barrier metal film223 of TaN has been formed, as shown in FIG. 31. By generating the Argas plasma, the barrier metal film 223 on the surface of the substrate203 is etched with Ar⁺ to flatten the barrier metal film 223. Also,denitrification is performed in which the nitrogen atoms (N) of the TaNin the superficial layer of the barrier metal film 223 are removed todecrease the nitrogen content of the superficial layer relative to theinterior of the matrix of the barrier metal film 223. As the barriermetal film 223, WN or TiN can also be applied.

[0603] The flattening of the barrier metal film 223 and itsdenitrification upon generation of the Ar gas plasma are carried outbefore formation of the aforementioned thin Cu film 216. The details ofthe flattening of the barrier metal film 223, and the details of thedenitrification of this film are the same as in the fifteenthembodiment, and relevant explanations are omitted.

[0604] With the foregoing metal film production apparatus, as in thefifteenth embodiment, the barrier metal film 223 can be in a two-layerstructure state without becoming thick, and yet the metal layer 223 acan retain adhesion to the thin Cu film 216, while the TaN layer 223 bcan prevent diffusion of Cu. Consequently, the thin Cu film 216 can beformed, with satisfactory adhesion, without diffusion into the substrate203, so that the Cu wiring process can be stabilized.

[0605] A metal film production method and a metal film productionapparatus according to the seventeenth embodiment of the presentinvention will be described with reference to FIG. 37. FIG. 37 is aschematic side view of the metal film production apparatus according tothe seventeenth embodiment of the present invention. The same members asthe members illustrated in FIGS. 2 and 7 are assigned the same numerals,and duplicate explanations are omitted.

[0606] The opening of an upper portion of a chamber 201 is closed with aceiling board 230, for example, made of a ceramic (an insulatingmaterial). An etched member 241 made of a metal (copper, Cu) is providedon a lower surface of the ceiling board 230, and the etched member 241is of a quadrangular pyramidal shape. Slit-shaped opening portions 242are formed at a plurality of locations (for example, four locations) inthe periphery of an upper part of the cylindrical portion of the chamber201, and one end of a tubular passage 243 is fixed to each of theopening portions 242. A tubular excitation chamber 244 made of aninsulator is provided halfway through the passage 243, and a coiledplasma antenna 245 is provided around the excitation chamber 244. Theplasma antenna 245 is connected to a matching instrument 248 and a powersource 249 to receive power. The plasma antenna 245, the matchinginstrument 248 and the power source 249 constitute plasma generationmeans.

[0607] A flow controller 246 is connected to the other end of thepassage 243, and a chlorine-containing source gas (a Cl₂ gas dilutedwith He or Ar to a chlorine concentration of ≦ 50%, preferably about10%) is supplied into the passage 243 via the flow controller 246. Byshooting electromagnetic waves from the plasma antenna 245 into theexcitation chamber 244, the Cl₂ gas is ionized to generate a Cl₂ gasplasma (source gas plasma) 247. Because of the generation of the Cl₂ gasplasma 247, excited chlorine is fed into the chamber 201 through theopening portion 42, whereupon the etched member 241 is etched withexcited chlorine.

[0608] With the above-described metal film production apparatus, thesource gas is supplied into the passage 243 via the flow controller 246and fed into the excitation chamber 244. By shooting electromagneticwaves from the plasma antenna 245 into the excitation chamber 244, theCl₂ gas is ionized to generate a Cl₂ gas plasma (source gas plasma) 247.Since a predetermined differential pressure has been established betweenthe pressure inside the chamber 201 and the pressure inside theexcitation chamber 244 by the vacuum device 208, the excited chlorine ofthe Cl₂ gas plasma 247 in the excitation chamber 244 is fed to theetched member 241 inside the chamber 201 through the opening portion242. The excited chlorine causes an etching reaction to the etchedmember 241, forming a precursor (M_(x)Cl_(y)) 215 inside the chamber201.

[0609] At this time, the etched member 241 is maintained at apredetermined temperature (e.g., 200 to 400° C.), which is higher thanthe temperature of the substrate 203, by a heater 250. The precursor(Cu_(x)Cl_(y)) 215 formed inside the chamber 201 is transported towardthe substrate 203 controlled to a lower temperature than the temperatureof the etched member 241. The precursor (Cu_(x)Cl_(y)) 215 transportedtoward the substrate 203 is converted into only Cu ions by a reductionreaction, and directed at the substrate 203 to form a thin Cu film 216on the surface of the substrate 203.

[0610] The reactions on this occasion are the same as in theaforementioned fifteenth embodiment, and the gases and etching productsthat have not been involved in the reactions are exhausted through anexhaust port 217.

[0611] With the above-described metal film production apparatus, the Cl₂gas plasma 247 is generated in the excitation chamber 244 isolated fromthe chamber 201. Thus, the substrate 203 is not exposed to the plasmaany more, and the substrate 203 becomes free from damage from theplasma. As the means for generating the Cl₂ gas plasma 247 in theexcitation chamber 244, it is possible to use microwaves, laser,electron rays, or synchrotron radiation. It is also permissible to formthe precursor by heating a metal filament to a high temperature. Theconstruction for isolating the Cl₂ gas plasma 247 from the substrate 203may be the provision of the excitation chamber 244 in the passage 243,or may be other construction, for example, the isolation of the chamber201.

[0612] The above-described metal film production apparatus is providedwith diluent gas nozzles 221, as diluent gas supply means, for supplyingan Ar gas, as a diluent gas, to the interior of the chamber 201 abovethe surface of the substrate 203. A coil-shaped surface treatment plasmaantenna 236 is provided on a trunk portion of the chamber 201. Amatching instrument 237 and a power source 238 are connected to thesurface treatment plasma antenna 236 to supply power. The Ar gas issupplied from the diluent gas nozzles 221, and electromagnetic waves areshot from the plasma antenna 236 into the chamber 201, whereby the Argas is ionized to generate an Ar gas plasma (surface treatment plasmageneration means). A bias power source 220 is connected to the supportplatform 202, and a bias voltage is applied thereto for supporting thesubstrate 203 on the support platform 202.

[0613] On the surface of the substrate 203 admitted into theabove-described metal film production apparatus, a barrier metal film223 of TaN has been formed, as shown in FIG. 31. By generating the Argas plasma, the barrier metal film 223 on the surface of the substrate203 is etched with Ar⁺ to flatten the barrier metal film 223. Also,denitrification is performed in which the nitrogen atoms (N) of the TaNin the superficial layer of the barrier metal film 223 are removed todecrease the nitrogen content of the superficial layer relative to theinterior of the matrix of the barrier metal film 223. As the barriermetal film 223, WN or TiN can also be applied.

[0614] The flattening of the barrier metal film 223 and itsdenitrification upon generation of the Ar gas plasma are carried outbefore formation of the aforementioned thin Cu film 216. The details ofthe flattening of the barrier metal film 223 and the denitrification ofthis film are the same as in the fifteenth embodiment, and relevantexplanations are omitted.

[0615] With the foregoing metal film production apparatus, the barriermetal film 223 can be in a two-layer structure state without becomingthick, and yet the metal layer 223 a (see FIG. 33) can retain adhesionto the thin Cu film 216, while the TaN layer 223 b (see FIG. 33) canprevent diffusion of Cu. Consequently, the thin Cu film 216 can beformed, with satisfactory adhesion, without diffusion into the substrate203, so that the Cu wiring process can be stabilized.

[0616] A barrier metal film production method and a barrier metal filmproduction apparatus according to the eighteenth embodiment of thepresent invention will be described with reference to FIG. 38. FIG. 38is a schematic side view of the metal film production apparatusaccording to the eighteenth embodiment of the present invention. Thesame members as the members illustrated in FIGS. 29, 34 and 37 areassigned the same numerals, and duplicate explanations are omitted.

[0617] Compared with the metal film production apparatus of thefifteenth embodiment shown in FIG. 29, the plasma antenna 209 is notprovided around the cylindrical portion of the chamber 201, and thematching instrument 210 and power source 211 are connected to the copperplate member 207 for supply of power to the copper plate member 207.With the above-described metal film production apparatus, the source gasis supplied from the nozzles 212 into the chamber 201, andelectromagnetic waves are shot from the copper plate member 207 into thechamber 201, the Cl₂ gas is ionized to generate a Cl₂ gas plasma (sourcegas plasma) 214. The Cl₂ gas plasma 214 causes an etching reaction tothe copper plate member 207, forming a precursor (Cu_(x)Cl_(y)) 215. Atthis time, the copper plate member 207 is maintained at a predeterminedtemperature (e.g., 200 to 400° C.), which is higher than the temperatureof the substrate 203, by the Cl₂ gas plasma 214.

[0618] The precursor (Cu_(x)Cl_(y)) 215 formed inside the chamber 201 istransported toward the substrate 203 controlled to a lower temperaturethan the temperature of the copper plate member 207. The precursor(Cu_(x)Cl_(y)) 215 transported toward the substrate 203 is convertedinto only Cu ions by a reduction reaction, and directed at the substrate203 to form a thin Cu film 216 on the surface of the substrate 203. Thereactions on this occasion are the same as in the aforementionedfifteenth embodiment, and the gases and etching products that have notbeen involved in the reactions are exhausted through an exhaust port217.

[0619] With the above-described metal film production apparatus, thecopper plate member 207 itself is applied as an electrode for plasmageneration. Thus, the plasma antenna 209 intended to prepare the thin Cufilm 216 need not be provided around the cylindrical portion of thechamber 201.

[0620] The above-described metal film production apparatus is providedwith diluent gas nozzles 221, as diluent gas supply means, for supplyingan Ar gas, as a diluent gas, to the interior of the chamber 201 abovethe surface of the substrate 203. Supply of the source gas through thenozzles 212 is cut off, the Ar gas is supplied from the diluent gasnozzles 221, and electromagnetic waves are shot from the copper platemember 207 into the chamber 201. By so doing, the Ar gas is ionized togenerate an Ar gas plasma (surface treatment plasma generation means). Abias power source 220 is connected to the support platform 202, and abias voltage is applied thereto for supporting the substrate 203 on thesupport platform 202.

[0621] On the surface of the substrate 203 admitted into theabove-described metal film production apparatus, a barrier metal film223 of TaN has been formed, as shown in FIG. 31. By generating the Argas plasma, the barrier metal film 223 on the surface of the substrate203 is etched with Ar⁺ to flatten the barrier metal film 223. Also,denitrification is performed in which the nitrogen atoms (N) of the TaNin the superficial layer of the barrier metal film 223 are removed todecrease the nitrogen content of the superficial layer relative to theinterior of the matrix of the barrier metal film 223. As the barriermetal film 223, WN or TiN can also be applied. As the surface treatmentplasma generation means, it is permissible to provide a coiled surfacetreatment plasma antenna on the trunk portion of the chamber 201, andsupply power via a matching instrument and a power source, therebygenerating an Ar gas plasma.

[0622] The flattening of the barrier metal film 223 and itsdenitrification upon generation of the Ar gas plasma are carried outbefore formation of the aforementioned thin Cu film 216. The details ofthe flattening of the barrier metal film 223 and the denitrification ofthis film are the same as in the fifteenth embodiment, and relevantexplanations are omitted.

[0623] With the foregoing metal film production apparatus, as in thefifteenth embodiment, the barrier metal film 223 can be in a two-layerstructure state without becoming thick, and the metal layer 223 a (seeFIG. 33) can retain adhesion to the thin Cu film 216, while the TaNlayer 223 b (see FIG. 33) can prevent diffusion of Cu. Consequently, thethin Cu film 216 can be formed, with satisfactory adhesion, withoutdiffusion into the substrate 203, so that the Cu wiring process can bestabilized.

[0624] Next, an example in which embodiments of the metal filmproduction method and metal film production apparatus according to thefirst aspect are provided in the barrier metal CVD 403 will be describedwith reference to FIG. 39. FIG. 39 schematically shows a side view ofthe metal film production apparatus according to the nineteenthembodiment of the present invention.

[0625] As shown in the drawing, a support platform 252 is provided nearthe bottom of a cylindrical chamber 251 made of, say, a ceramic (aninsulating material), and a substrate 253 is placed on the supportplatform 252. Temperature control means 256 equipped with a heater 254and refrigerant flow-through means 255 is provided in the supportplatform 252 so that the support platform 252 is controlled to apredetermined temperature (for example, a temperature at which thesubstrate 253 is maintained at 100 to 200° C.) by the temperaturecontrol means 256.

[0626] An upper surface of the chamber 251 is an opening, which isclosed with a metal member 257, as an etched member, made of a metal(e.g., W, Ti, Ta, or TiSi). The interior of the chamber 251 closed withthe metal member 257 is maintained at a predetermined pressure by avacuum device 258. A plasma antenna 259, as a coiled winding antenna ofplasma generation means, is provided around a cylindrical portion of thechamber 251. A matching instrument 260 and a power source 261 areconnected to the plasma antenna 259 to supply power.

[0627] Nozzles 262 for supplying a source gas (a Cl₂ gas diluted with Heor Ar to a chlorine concentration of ≦ 50%, preferably about 10%),containing chlorine as a halogen, to the interior of the chamber 251 areconnected to the cylindrical portion of the chamber 251 below the metalmember 257. The nozzle 262 is open toward the horizontal, and is fedwith the source gas via a flow controller 263 (halogen gas supplymeans). Fluorine (F), bromine (Br) or iodine (I) can also be applied asthe halogen to be incorporated into the source gas.

[0628] Slit-shaped opening portions 264 are formed at a plurality oflocations (for example, four locations) in the periphery of a lower partof the cylindrical portion of the chamber 251, and one end of a tubularpassage 265 is fixed to each of the opening portions 264. A tubularexcitation chamber 266 made of an insulator is provided halfway throughthe passage 265, and a coiled plasma antenna 267 is provided around theexcitation chamber 266. The plasma antenna 267 is connected to amatching instrument 268 and a power source 269 to receive power. Theplasma antenna 267, the matching instrument 268 and the power source 269constitute excitation means. A flow controller 270 is connected to theother end of the passage 265, and an ammonia gas (NH₃ gas) as anitrogen-containing gas is supplied into the passage 265 via the flowcontroller 270.

[0629] With the above-described metal film production apparatus, thesource gas is supplied through the nozzles 262 to the interior of thechamber 251, and electromagnetic waves are shot from the plasma antenna259 into the chamber 251. As a result, the Cl₂ gas is ionized togenerate a Cl₂ gas plasma (source gas plasma) 271. The Cl₂ gas plasma271 causes an etching reaction to the metal member 257, forming aprecursor (M_(x)Cl_(y): M is a metal such as W, Ti, Ta or TiSi) 272.

[0630] Separately, the NH₃ gas is supplied into the passage 265 via theflow controller 270 and fed into the excitation chamber 266. By shootingelectromagnetic waves from the plasma antenna 267 into the excitationchamber 266, the NH₃ gas is ionized to generate an NH₃ gas plasma 263.Since a predetermined differential pressure has been established betweenthe pressure inside the chamber 251 and the pressure inside theexcitation chamber 266 by the vacuum device 258, the excited ammonia ofthe NH₃ gas plasma 273 in the excitation chamber 266 is fed to theprecursor (M_(x)Cl_(y)) 272 inside the chamber 251 through the openingportion 264.

[0631] That is, excitation means for exciting the nitrogen-containinggas in the excitation chamber 266 isolated from the chamber 251 isconstructed. Because of this construction, the metal component of theprecursor (M_(x)Cl_(y)) 272 and ammonia react to form a metal nitride(MN) (formation means). At this time, the metal member 257 and theexcitation chamber 266 are maintained by the plasmas at predeterminedtemperatures (e.g., 200 to 400° C.) which are higher than thetemperature of the substrate 253.

[0632] The metal nitride (MN) formed within the chamber 251 istransported toward the substrate 253 controlled to a low temperature,whereby a thin MN film 274 (a TaN film if the metal member 257 of Ta isapplied) is formed on the surface of the substrate 253.

[0633] The reaction for formation of the thin MN film 274 can beexpressed by:

2MCl+2NH₃→2MN↓+HCl↑+2H₂↑

[0634] The gases and the etching products that have not been involved inthe reactions are exhausted through an exhaust port 277.

[0635] The source gas has been described, with the Cl₂ gas diluted with,say, He or Ar taken as an example. However, the Cl₂ gas can be usedalone, or an HCl gas can also be applied. When the HCl gas is applied,an HCl gas plasma is generated as the source gas plasma. Thus, thesource gas may be any gas containing chlorine, and a gas mixture of anHCl gas and a Cl₂ gas is also usable. As the material for the metalmember 257, it is possible to use an industrially applicable metal suchas Ag, Au, Pt or Si. Further, the NH₃ gas is supplied into the passage265 and fed into the excitation chamber 266. At the same time,electromagnetic waves are shot from the plasma antenna 267 into theexcitation chamber 266 to generate the NH₃ gas plasma 263. However, anNH₃ gas plasma can be generated within the chamber 251 by supplying anNH₃ gas into the chamber 251 and supplying power to the plasma antenna259. In this case, the chamber 265, excitation chamber 266, plasmaantenna 267, matching instrument 268 and power source 269 can beomitted.

[0636] With the above-described metal film production apparatus, themetal is formed by plasmas to produce the thin MN film 274 as thebarrier metal film. Thus, the barrier metal film can be formed uniformlyto a small thickness. Consequently, the barrier metal film can be formedhighly accurately at a high speed with excellent burial properties in avery small thickness even to the interior of a tiny depression, forexample, several hundred nanometers wide, which has been provided in thesubstrate 253.

[0637] The above-described metal film production apparatus is providedwith diluent gas nozzles 276, as diluent gas supply means, for supplyingan Ar gas, as a diluent gas, to the interior of the chamber 251 abovethe surface of the substrate 253. The Ar gas is supplied from thediluent gas nozzles 276, and electromagnetic waves are shot from theplasma antenna 259 into the chamber 251, whereby the Ar gas is ionizedto generate an Ar gas plasma (surface treatment plasma generationmeans). A bias power source 277 is connected to the support platform252, and a bias voltage is applied thereto for supporting the substrate253 on the support platform 252.

[0638] With the above-described metal film production apparatus, thethin MN film 274 as a barrier metal film is formed, whereafter an Ar gasplasma is generated. By generating the Ar gas plasma, the barrier metalfilm on the surface of the substrate 253 is etched with Ar⁺ to flattenthe barrier metal film. Also, denitrification is performed in which thenitrogen atoms (N) of the TaN in the superficial layer of the barriermetal film are removed. After flattening of the barrier metal film andthe removal of the nitrogen atoms (N) of the TaN in the superficiallayer for denitrification, a thin copper (Cu) film or a thin aluminum(Al) film is formed on the barrier metal film by a film forming device.The details of the flattening of the barrier metal film and thedenitrification of this film upon generation of the Ar gas plasma arethe same as in the fifteenth embodiment. Thus, relevant explanations areomitted.

[0639] With the foregoing metal film production apparatus, as in thefifteenth embodiment, the barrier metal film can be in a two-layerstructure state without becoming thick, and the resulting metal layercan retain adhesion to a thin metal film formed by film formation in thesubsequent step. Whereas the TaN layer can prevent diffusion of metalduring film formation in the subsequent step. Consequently, the thinmetal film (thin Cu film) during film formation in the subsequent stepcan be formed, with satisfactory adhesion, without diffusion into thesubstrate 253, so that the Cu wiring process can be stabilized.

[0640] The construction of the metal film production apparatus forproducing the barrier metal film may employ a device of the typegenerating a capacitive coupling plasma, or a device of the remote typewhich generates a plasma in a manner isolated from a film formationchamber.

[0641] Next, the second aspect of the present invention will bedescribed. According to the second aspect, the barrier metal film of TaNis subjected to a surface treatment in which this film is reacted in areducing gas (e.g. hydrogen gas) atmosphere (a hydrogen gas plasma) toremove the nitrogen atoms in the superficial layer of the barrier metalfilm, thereby decreasing the nitrogen content of the superficial layerrelative to the interior of the matrix of the barrier metal film (thistreatment will be referred to hereinafter as denitrification). Thedenitrification brings a state in which a film of the metal (Ta) issubstantially formed in the superficial layer of the single-layerbarrier metal film. In this manner, a barrier metal film is producedhighly efficiently and reliably in a thin film condition, with thediffusion of the metal being prevented and the adhesion to the metalbeing maintained.

[0642] As the reducing gas, a nitrogen gas as well as the hydrogen gascan be applied, or a carbon monoxide gas can also be applied. If thecarbon monoxide gas is used, denitrification can be carried out in acarbon monoxide gas atmosphere, without generation of plasma.

[0643] The concrete construction of the apparatus according to thesecond aspect of the invention may be as follows: A source gascontaining a halogen (e.g., a chlorine-containing gas) is supplied tothe interior of a chamber between a substrate and an etched member ofTa, and an atmosphere within the chamber is converted into a plasma togenerate a chlorine gas plasma. The etched member is etched with thechlorine gas plasma to form a precursor comprising the Ta componentcontained in the etched member and the chlorine gas. Also, anitrogen-containing gas is excited, and TaN, a metal nitride, is formedupon reaction between the excited nitrogen and the precursor. Theresulting TaN is formed as a film on the substrate kept at a lowtemperature to form a barrier metal film. This process is performedusing a barrier metal film production apparatus. After the barrier metalfilm is produced in this manner, a hydrogen gas plasma (or a nitrogengas plasma) is generated within the chamber to react radical hydrogenwith nitrogen, performing denitrification. That is, the barrier metalfilm production apparatus shown in FIG. 39 can be applied.

[0644] Alternatively, the concrete construction of the apparatus of thesecond aspect may be as follows: A chlorine gas is supplied into thechamber, and an atmosphere within the chamber is converted into a plasmato generate a chlorine gas plasma. An etched member made of copper (Cu)is etched with the chlorine gas plasma to form a precursor comprisingthe Cu component contained in the etched member and chlorine inside thechamber. The temperature of the substrate is rendered lower than thetemperature of the etched member to form a film of the Cu component ofthe precursor on the substrate. This process is performed using a metalfilm forming device. Before the substrate having a barrier metal film ofTaN formed thereon is housed in the chamber and the Cu component isformed as a film thereon, a hydrogen gas plasma (or a nitrogen gasplasma) is generated within the chamber to react radical hydrogen withnitrogen, performing denitrification. That is, the metal film productionapparatus shown, for example, in FIGS. 29, 34, 37 and 38 can be applied.

[0645] Embodiments of the metal film production method and metal filmproduction apparatus according to the second aspect will be described,with the provision of the apparatus in the Cu-CVD 404 (see FIG. 28)being taken as an example.

[0646]FIG. 40 shows the conceptual construction of a metal filmproduction apparatus according to the twentieth embodiment of thepresent invention. FIG. 41 shows the concept status of the barrier metalfilm in denitrification. The illustrated metal film production apparatushas the conceptual construction of the metal film production apparatusaccording to the fifteenth embodiment shown in FIG. 29, in which the gassupplied through the nozzle 21 is different. Thus, the formation of thethin Cu film in the metal film production apparatus is the same, and itsexplanation is omitted hereinbelow.

[0647] As shown in FIG. 40, reducing gas nozzles 225 are provided, asreducing gas supply means, for supplying a hydrogen gas (H₂ gas) as areducing gas, to the interior of a chamber 201 above the surface of asubstrate 203. The H₂ gas is supplied from the reducing gas nozzles 225,and electromagnetic waves are shot from a plasma antenna 209 into thechamber 201, whereby the H₂ gas is ionized to generate an H₂ gas plasma(surface treatment means). On the surface of the substrate 203 admittedinto the illustrated metal film production apparatus, a barrier metalfilm 223 of TaN (see FIG. 31) has been formed. Upon generation of the H₂gas plasma, hydrogen radicals H* react with the nitrogen atoms (N) ofthe TaN in the superficial layer of the substrate 203, forming ammoniaNH₃, which is exhausted. Thus, the nitrogen atoms (N) in the superficiallayer are removed to decrease the nitrogen content of the superficiallayer relative to the interior of the matrix of the barrier metal film223 (denitrification).

[0648] The denitrification of the barrier metal film 223 (see FIG. 31)caused by generation of the H₂ gas plasma is performed before formationof the thin Cu film 216 explained in the fifteenth embodiment of FIG.29. That is, when the substrate 203 having the barrier metal film 223 ofTaN (see FIG. 31) formed thereon is admitted onto a support platform202, the H₂ gas is supplied from the reducing gas nozzles 225 prior tothe formation of the thin Cu film 216 (see FIG. 29). At the same time,electromagnetic waves are shot from the plasma antenna 209 into thechamber 201, whereby the H₂ gas plasma is generated.

[0649] Upon generation of the H₂ gas plasma, hydrogen radicals H* reactwith the nitrogen atoms (N) of the TaN in the superficial layer of thesubstrate 203, forming ammonia NH₃, which is exhausted. The hydrogenradicals H* do not affect the metal, but react with only the nitrogenatoms (N), thereby forming ammonia NH₃.

[0650] That is, the reaction

N+3H*→NH₃

[0651] forms ammonia NH₃, which is exhausted.

[0652] As shown in FIG. 41, the barrier metal film 223 comprises Ta andN in an amorphous state. In this state, hydrogen radicals H* react withN, forming ammonia NH₃, which is exhausted. In this manner, thesuperficial layer of the barrier metal film 223 (for example, up to ahalf, preferably about a third, of the entire film thickness) isdenitrified. As a result, there emerges the barrier metal film 223 of atwo-layer structure, a metal layer 223 a substantially composed of Ta,and a TaN layer 223 b, as shown in FIG. 33. On this occasion, the entirefilm thickness of the barrier metal film 223 remains the film thicknessconstructed by the single layer.

[0653] Hydrogen radicals H* have a short life and penetrate narrowsites. Thus, the pressure inside the chamber 201 is lowered to decreasethe density, or the temperature of the substrate 203 is controlled,thereby making it possible to increase hydrogen radicals H* (preventthem from colliding with each other), or to control the depth of themetal layer 223 a composed substantially of Ta (see FIG. 33). Setting ofthe pressure can be performed by increasing the mean free path (MFP)which is the value of the distance traveled by a hydrogen radical H*before collision. Normally, the distance from the center of the plasmato the substrate 203 depends on the apparatus. To increase the mean freepath, control is exercised, with the pressure inside the chamber 201being lowered. If the apparatus has the support platform 202 movableupward and downward, the support platform 202 is raised, without a fallin the pressure, to bring the substrate 203 close to the center of theplasma, whereby the mean free path can be increased relatively.

[0654] With the foregoing metal film production apparatus, the hydrogengas plasma is generated within the chamber 201 accommodating thesubstrate 203 having the barrier metal film 223 formed thereon. Thehydrogen radicals H* take part in denitrification in which they reactwith the nitrogen atoms (N), forming ammonia NH₃, which is exhausted.Thus, there can appear the barrier metal film 223 with a two-layerstructure, i.e., the metal layer 223 a composed substantially of Ta (seeFIG. 33) and the TaN layer 223 b (see FIG. 33). Moreover, the entirefilm thickness can remain the single-layer film thickness. Hence, thebarrier metal film 223 can be in a two-layer structure state withoutbecoming thick, and yet the metal layer 223 a (see FIG. 33) can retainadhesion to the thin Cu film 216 (see FIG. 29), while the TaN layer 223b (see FIG. 33) can prevent diffusion of Cu. Consequently, the thin Cufilm 216 (see FIG. 29) can be formed, with satisfactory adhesion,without diffusion into the substrate 203, so that the Cu wiring processcan be stabilized. In addition, denitrification can be carried out withhigh efficiency.

[0655] The hydrogen gas has been taken as an example of the reducing gasfor the purpose of explanation. In the case of the metal film productionapparatus in which a hydrogen atmosphere is not usable, a nitrogen gascan be used as the reducing gas. In this case, a nitrogen gas plasma isgenerated, whereupon N* reacts with the nitrogen atoms (N) of thebarrier metal film 223. As a result, N+N*→N₂, which is exhausted. Theuse of the nitrogen gas enables denitrification to take place easily,even if a limitation is imposed on the use of the reducing gas.

[0656] Alternatively, a carbon monoxide gas can be used as the reducinggas. In this case, no plasma is generated, and in the unchangedatmosphere, CO reacts with the nitrogen atoms (N) of the barrier metalfilm 223, as in 2N+2CO→2CN+O₂, which are exhausted. The use of thecarbon monoxide gas enables denitrification to take place, simply bytemperature control of the substrate 203 without generation of a plasma.Thus, consumption of power can be decreased.

[0657] The twentieth embodiment described above can be applied to themetal film production apparatuses of the sixteenth to eighteenthembodiments shown in FIGS. 34, 37 and 38. It is also applicable to thebarrier metal film production apparatus of the nineteenth embodimentshown in FIG. 39. It is also possible to combine the flattening of thesurface with Ar⁺ upon generation of the Ar gas plasma in the fifteenthto nineteenth embodiments with denitrification using the reducing gasplasma. In this case, an Ar gas and a reducing gas may be mixed andsupplied into the chamber 1, or an Ar gas and a reducing gas may besupplied sequentially.

[0658] Next, the third aspect of the present invention will bedescribed. According to the third aspect, a barrier metal film of TaN issubjected to a treatment for etching the surface and forming nuclei ofsilicon atoms by use of a plasma of a silicon-containing gas (forexample, silane, SiH₄, a hydride of silicon). Silicon, which is not aforeign matter, has good adhesion to a metal, and the formation ofnuclei of silicon atoms on the surface can increase adhesion between themetal of a barrier metal film and a metal to be formed as a filmthereon. By this method, a barrier metal film preventing diffusion of ametal and retaining adhesion to the metal is produced with goodefficiency and without deterioration of performance.

[0659] As the silicon-containing gas, a disilane (Si₂H₆) gas or atrisilane (Si₃H₈) can be used in addition to the SiH₄ gas. If hydrogencannot be used, an SiCl₄ gas, an SiH₂Cl₂ gas or an SiHCl₃ gas can beapplied. Any such gas may be diluted with a diluent gas and supplied. Bycontrolling the dilution ratio or the flow rate of the gas, orcontrolling the power of its plasma, it becomes possible to control thedepth of etching on the surface or the sizes of the nuclei of siliconatoms.

[0660] A concrete apparatus construction according to the third aspectof the invention may be as follows: Using a barrier metal filmproduction apparatus, a source gas containing a halogen (e.g., achlorine-containing gas) is supplied to the interior of a chamberbetween a substrate and an etched member of Ta, and an atmosphere withinthe chamber is converted into a plasma to generate a chlorine gasplasma. The etched member is etched with the chlorine gas plasma to forma precursor comprising the Ta component contained in the etched memberand the chlorine gas. Also, a nitrogen-containing gas is excited, andTaN, a metal nitride, is formed upon reaction between the excitednitrogen and the precursor. The resulting TaN is formed as a film on thesubstrate kept at a low temperature to form a barrier metal film. Afterthe barrier metal film is produced in this manner, an SiH₄ gas plasma, agas containing silicon, is generated within the chamber to form crystalgrains of Si. That is, a barrier metal film production apparatus shown,for example, in FIG. 39 can be applied.

[0661] Alternatively, a concrete apparatus construction according to thethird aspect of the invention may be as follows: A chlorine gas issupplied into the chamber, and an atmosphere within the chamber isconverted into a plasma to generate a chlorine gas plasma. An etchedmember made of copper (Cu) is etched with the chlorine gas plasma toform a precursor comprising the Cu component contained in the etchedmember and chlorine inside the chamber. The temperature of the substrateis rendered lower than the temperature of the etched member to form afilm of the Cu component of the precursor on the substrate. This processis performed using a metal film forming device. The substrate having abarrier metal film of TaN formed thereon is housed in the chamber.Before the Cu component is formed as a film thereon, an SiH₄ gas plasma,a plasma of a silicon-containing gas, is generated within the chamber toform crystal grains of Si. That is, the metal film production apparatusshown, for example, in FIG. 29, 34, 37 or 38 can be applied.

[0662] An embodiment of the metal film production method and metal filmproduction apparatus according to the third aspect will be described,with the provision of the apparatus in the Cu-CVD 404 (see FIG. 28)being taken as an example.

[0663]FIG. 42 shows the conceptual construction of a metal filmproduction apparatus according to the twenty-first embodiment of thepresent invention. FIG. 43 shows the concept status of a barrier metalfilm in the formation of nuclei of Si. The illustrated metal filmproduction apparatus has the conceptual construction of the metal filmproduction apparatus according to the fifteenth embodiment shown in FIG.29, in which the gas supplied through the nozzles 21 is made different.Thus, the formation of the thin Cu film in the metal film productionapparatus is the same, and its explanation is omitted hereinbelow.

[0664] As shown in FIG. 42, silicon-containing gas nozzles 228 areprovided, as silicon-containing gas supply means, for supplying a silanegas (SiH₄ gas), as a gas containing silicon, to the interior of achamber 201 above the surface of a substrate 203. An SiH₄ gas dilutedwith hydrogen is supplied through the silicon-containing gas nozzles228, and electromagnetic waves are shot from a plasma antenna 209 intothe chamber 201, whereby the hydrogen-diluted SiH₄ gas is ionized togenerate an SiH₄ gas plasma (surface treatment plasma means). On thesurface of the substrate 203 admitted into the illustrated metal filmproduction apparatus, a barrier metal film 223 of TaN (see FIG. 31) hasbeen formed. Generation of the SiH₄ gas plasma results in the growth ofcrystal grains of Si and the appearance of H₂. While film formation isproceeding, crystal grains of Si are formed as nuclei on the superficiallayer of the substrate 203 by the etching action of H₂.

[0665] The formation of the nuclei of Si upon generation of the SiH₄ gasplasma is performed before formation of the thin Cu film 216 explainedin the fifteenth embodiment of FIG. 29. That is, when the substrate 203having the barrier metal film 223 of TaN (see FIG. 31) formed there onis admitted onto the support platform 202, a hydrogen-diluted SiH₄ gasis supplied through the silicon-containing gas nozzles 228 prior to theformation of the thin Cu film 216 (see FIG. 29). Also, electromagneticwaves are shot from the plasma antenna 209 into the chamber 201 togenerate an SiH₄ gas plasma. The ratio of SiH₄ to hydrogen in thehydrogen-diluted SiH₄ gas is set, for example, as follows: SiH₄/hydrogen≦ 5/100. As the diluent gas, argon, helium, neon or other diluent gascan be applied in addition to hydrogen.

[0666] When the SiH₄ gas plasma is generated, the reaction

SiH₄→Si+H₂

[0667] proceeds. As a result, while film formation is proceeding,crystal grains of Si are formed as nuclei on the superficial layer ofthe barrier metal film 223 by the etching action of H₂, as shown in FIG.43. The sizes of the nuclei of Si can be controlled appropriately bycontrolling the conditions for the plasma, the ratio of hydrogendilution, the flow rate of the gas, etc. The etching action of H₂removes the nitrogen atoms (N) of the barrier metal film 223, and canbring the state of the barrier metal film 223 having a two-layerstructure, a metal layer 223 a substantially composed of Ta (see FIG.33), and a TaN layer 223 b (see FIG. 33).

[0668] Since the SiH₄ gas is diluted with hydrogen, the crystallinity ofSi can be improved, and its nuclei are easy to form. Silicon, which isnot a foreign matter, has good adhesion to Ta and Cu, and the formationof nuclei of Si on the surface of the barrier metal film 223 canincrease adhesion between Ta of the barrier metal film 223 and Cu to beformed as a film thereon. By this method, a barrier metal film 223preventing diffusion of the metal and retaining adhesion to the metal isproduced with good efficiency and without deterioration of performance.

[0669] With the above-described metal film production apparatus, theSiH₄ gas plasma is generated within the chamber 201 accommodating thesubstrate 203 having the barrier metal film 223 formed thereon, wherebycrystal grains of Si are formed as nuclei on the superficial layer ofthe barrier metal film 223. Thus, adhesion to Ta and Cu can be improved.Consequently, the barrier metal film 223 can be formed with satisfactoryadhesion and anti-diffusion properties without becoming thick, so thatthe Cu wiring process can be stabilized.

[0670] The twenty-first embodiment described above can be applied to themetal film production apparatuses of the sixteenth to eighteenthembodiments shown in FIGS. 34, 37 and 38. It is also applicable to thebarrier metal film production apparatus of the nineteenth embodimentshown in FIG. 39. It is also possible to combine the flattening of thesurface with Ar⁺ upon generation of the Ar gas plasma in the fifteenthto nineteenth embodiments with the formation of crystal grains of Si asnuclei on the superficial layer of the barrier metal film 223. In thiscase, a common nozzle can be used by diluting an SiH₄ gas with an Argas, and the flattening of the surface and the formation of Si nucleican be easily switched by controlling the flow rate of the Ar gas.

[0671] While the present invention has been described by the foregoingembodiments, it is to be understood that the invention is not limitedthereby, but may be varied in many other ways. Such variations are notto be regarded as a departure from the spirit and scope of theinvention, and all such modifications as would be obvious to one skilledin the art are intended to be included within the scope of the appendedclaims.

What is claimed is:
 1. A barrier metal film production apparatus,comprising: a chamber accommodating a substrate; a metallic etchedmember provided in the chamber at a position opposed to the substrate;source gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember; plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas;excitation means for exciting a nitrogen-containing gas in a mannerisolated from the chamber; formation means for forming a metal nitrideupon reaction between nitrogen excited by the excitation means and theprecursor; and control means which makes a temperature of the substratelower than a temperature of the formation means to form the metalnitride as a film on the substrate.
 2. A barrier metal film productionapparatus, comprising: a chamber accommodating a substrate; a metallicetched member provided in the chamber at a position opposed to thesubstrate; source gas supply means for supplying a source gas containinga halogen to an interior of the chamber between the substrate and theetched member; plasma generation means which converts an atmospherewithin the chamber into a plasma to generate a source gas plasma so thatthe etched member is etched with the source gas plasma to form aprecursor from a metal component contained in the etched member and thesource gas; excitation means for exciting a nitrogen-containing gas in amanner isolated from the chamber; formation means for forming a metalnitride upon reaction between nitrogen excited by the excitation meansand the precursor; and control means which makes a temperature of thesubstrate lower than a temperature of the formation means to form themetal nitride as a film on the substrate, and after film formation ofthe metal nitride, stops supply of the nitrogen-containing gas, andmakes the temperature of the substrate lower than a temperature of theetched member to form the metal component of the precursor as a film onthe metal nitride on the substrate.
 3. A barrier metal film productionapparatus, comprising: a chamber accommodating a substrate; a metallicetched member provided in the chamber at a position opposed to thesubstrate; source gas supply means for supplying a source gas containinga halogen to an interior of the chamber between the substrate and theetched member; nitrogen-containing gas supply means for supplying anitrogen-containing gas to an interior of the chamber between thesubstrate and the etched member; plasma generation means which convertsan atmosphere within the chamber into a plasma to generate a source gasplasma and a nitrogen-containing gas plasma so that the etched member isetched with the source gas plasma to form a precursor from a metalcomponent contained in the etched member and the source gas, and that ametal nitride is formed upon reaction between nitrogen and theprecursor; and control means which makes a temperature of the substratelower than a temperature of the etched member to form the metal nitrideas a film on the substrate.
 4. A barrier metal film productionapparatus, comprising: a chamber accommodating a substrate; a metallicetched member provided in the chamber at a position opposed to thesubstrate; source gas supply means for supplying a source gas containinga halogen to an interior of the chamber between the substrate and theetched member; nitrogen-containing gas supply means for supplying anitrogen-containing gas to an interior of the chamber between thesubstrate and the etched member; plasma generation means which convertsan atmosphere within the chamber into a plasma to generate a source gasplasma and a nitrogen-containing gas plasma so that the etched member isetched with the source gas plasma to form a precursor from a metalcomponent contained in the etched member and the source gas, and that ametal nitride is formed upon reaction between nitrogen and theprecursor; and control means which makes a temperature of the substratelower than a temperature of the etched member to form the metal nitrideas a film on the substrate, and then stops supply of thenitrogen-containing gas, and makes the temperature of the substratelower than the temperature of the etched member to form the metalcomponent of the precursor as a film on the metal nitride on thesubstrate.
 5. The barrier metal film production apparatus of any one ofclaims 1 to 4, wherein the plasma generation means includes a coiledwinding antenna disposed around the chamber.
 6. The barrier metal filmproduction apparatus of any one of claims 1 to 4, wherein the source gascontaining the halogen is the source gas containing chlorine.
 7. Thebarrier metal film production apparatus of any one of claims 1 to 4,wherein the nitrogen-containing gas is a gas containing ammonia.
 8. Thebarrier metal film production apparatus of any one of claims 1 to 4,wherein the etched member is made of tantalum, tungsten, titanium orsilicon which is a halide-forming metal.
 9. A barrier metal filmproduction method comprising: supplying a source gas containing ahalogen to an interior of a chamber between a substrate and a metallicetched member; converting an atmosphere within the chamber into a plasmato generate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas; exciting anitrogen-containing gas in a manner isolated from the chamberaccommodating the substrate; forming a metal nitride upon reactionbetween excited nitrogen and the precursor; and making a temperature ofthe substrate lower than a temperature of means for formation of themetal nitride to form the metal nitride as a film on the substrate. 10.A barrier metal film production method comprising: supplying a sourcegas containing a halogen to an interior of a chamber between a substrateand a metallic etched member; converting an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas;exciting a nitrogen-containing gas in a manner isolated from the chamberaccommodating the substrate; forming a metal nitride upon reactionbetween excited nitrogen and the precursor; and making a temperature ofthe substrate lower than a temperature of means for formation of themetal nitride to form the metal nitride as a film on the substrate; andafter film formation of the metal nitride, stopping supply of thenitrogen-containing gas, and making the temperature of the substratelower than a temperature of the etched member to form the metalcomponent of the precursor as a film on the metal nitride on thesubstrate.
 11. A barrier metal film production method comprising:supplying a source gas containing a halogen and a nitrogen-containinggas to an interior of a chamber between a substrate and a metallicetched member; converting an atmosphere within the chamber into a plasmato generate a source gas plasma and a nitrogen-containing gas plasma sothat the etched member is etched with the source gas plasma to form aprecursor from a metal component contained in the etched member and thesource gas, and that a metal nitride is formed upon reaction betweennitrogen and the precursor; and making a temperature of the substratelower than a temperature of the etched member to form the metal nitrideas a film on the substrate.
 12. A barrier metal film production methodcomprising: supplying a source gas containing a halogen and anitrogen-containing gas to an interior of a chamber between a substrateand a metallic etched member; converting an atmosphere within thechamber into a plasma to generate a source gas plasma and anitrogen-containing gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and that a metalnitride is formed upon reaction between nitrogen and the precursor;making a temperature of the substrate lower than a temperature of theetched member to form the metal nitride as a film on the substrate; andafter film formation of the metal nitride, stopping supply of thenitrogen-containing gas, and making the temperature of the substratelower than the temperature of the etched member to form the metalcomponent of the precursor as a film on the metal nitride on thesubstrate.
 13. A barrier metal film production apparatus, comprising: achamber accommodating a substrate; a metallic etched member provided inthe chamber at a position opposed to the substrate; source gas supplymeans for supplying a source gas containing a halogen into the chamber;nitrogen-containing gas supply means for supplying a gas containingnitrogen into the chamber; plasma generation means which converts anatmosphere within the chamber into a plasma to generate a source gasplasma so that the etched member is etched with the source gas plasma toform a precursor from a metal component contained in the etched memberand the source gas, and which converts the atmosphere within the chamberinto a plasma to generate a nitrogen-containing gas plasma so that ametal nitride is formed upon reaction between nitrogen and theprecursor; control means which makes a temperature of the substratelower than a temperature of the plasma generation means to form themetal nitride as a barrier metal film on a surface of the substrate;diluent gas supply means for supplying a diluent gas to a site above thesurface of the substrate; and surface treatment plasma generation meansfor performing a surface treatment which converts the atmosphere withinthe chamber into a plasma to generate a diluent gas plasma so thatnitrogen atoms in a superficial layer of the barrier metal film areremoved by the diluent gas plasma to decrease a nitrogen content of thesuperficial layer relative to an interior of a matrix of the barriermetal film.
 14. The barrier metal film production apparatus of claim 13,further comprising: oxygen gas supply means for supplying an oxygen gasinto the chamber immediately before formation of the most superficiallayer of the barrier metal film is completed; and oxygen plasmageneration means which converts the atmosphere within the chamber into aplasma to generate an oxygen gas plasma so that an oxide layer is formedon the most superficial layer of the barrier metal film.
 15. A barriermetal film production apparatus, comprising: a chamber accommodating asubstrate; a metallic etched member provided in the chamber at aposition opposed to the substrate; source gas supply means for supplyinga source gas containing a halogen into the chamber; nitrogen-containinggas supply means for supplying a gas containing nitrogen into thechamber; plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas, andwhich converts the atmosphere within the chamber into a plasma togenerate a nitrogen-containing gas plasma so that a metal nitride isformed upon reaction between nitrogen and the precursor; control meanswhich makes a temperature of the substrate lower than a temperature ofthe plasma generation means to form the metal nitride as a barrier metalfilm on a surface of the substrate; oxygen gas supply means forsupplying an oxygen gas to a site above the surface of the substrate;and oxygen plasma generation means for performing a surface treatmentwhich converts the atmosphere within the chamber into a plasma togenerate an oxygen gas plasma so that nitrogen atoms in a superficiallayer of the barrier metal film are removed by the oxygen gas plasma todecrease a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film, and at the same time,forming an oxide layer on the most superficial layer of the barriermetal film.
 16. A barrier metal film production apparatus, comprising: achamber accommodating a substrate; a metallic etched member provided inthe chamber at a position opposed to the substrate; source gas supplymeans for supplying a source gas containing a halogen into the chamber;nitrogen-containing gas supply means for supplying a gas containingnitrogen into the chamber; plasma generation means which converts anatmosphere within the chamber into a plasma to generate a source gasplasma so that the etched member is etched with the source gas plasma toform a precursor from a metal component contained in the etched memberand the source gas, and which converts the atmosphere within the chamberinto a plasma to generate a nitrogen-containing gas plasma so that ametal nitride is formed upon reaction between nitrogen and theprecursor; control means which makes a temperature of the substratelower than a temperature of the plasma generation means to form themetal nitride as a film, for use as a barrier metal film, on a surfaceof the substrate; oxygen gas supply means for supplying an oxygen gasinto the chamber immediately before formation of the most superficiallayer of the barrier metal film is completed; and oxygen plasmageneration means which converts the atmosphere within the chamber into aplasma to generate an oxygen gas plasma so that an oxide layer is formedon the most superficial layer of the barrier metal film.
 17. A barriermetal film production apparatus, comprising: a chamber accommodating asubstrate; a metallic etched member provided in the chamber at aposition opposed to the substrate; source gas supply means for supplyinga source gas containing a halogen into the chamber; nitrogen-containinggas supply means for supplying a gas containing nitrogen into thechamber; plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas, andwhich converts the atmosphere within the chamber into a plasma togenerate a nitrogen-containing gas plasma so that a metal nitride isformed upon reaction between nitrogen and the precursor; control meanswhich makes a temperature of the substrate lower than a temperature ofthe plasma generation means to form the metal nitride as a film on asurface of the substrate, then makes the temperature of the substratelower than the temperature of the plasma generation means and stopssupply of the gas containing nitrogen from the nitrogen-containing gassupply means, thereby forming the metal component of the precursor as afilm on the metal nitride for use as a barrier metal film; oxygen gassupply means for supplying an oxygen gas into the chamber immediatelybefore formation of the most superficial layer of the barrier metal filmis completed; and oxygen plasma generation means which converts theatmosphere within the chamber into a plasma to generate an oxygen gasplasma so that an oxide layer is formed on the most superficial layer ofthe barrier metal film.
 18. A barrier metal film production apparatus,comprising: a chamber accommodating a substrate; a metallic etchedmember provided in the chamber at a position opposed to the substrate;source gas supply means for supplying a source gas containing a halogeninto the chamber; plasma generation means which converts an atmospherewithin the chamber into a plasma to generate a source gas plasma so thatthe etched member is etched with the source gas plasma to form aprecursor from a metal component contained in the etched member and thesource gas; excitation means for exciting a gas containing nitrogen in amanner isolated from the chamber; formation means for forming a metalnitride upon reaction between nitrogen excited by the excitation meansand the precursor; control means which makes a temperature of thesubstrate lower than a temperature of the formation means to form themetal nitride as a film on the substrate for use as a barrier metalfilm; oxygen gas supply means for supplying an oxygen gas into thechamber immediately before formation of the most superficial layer ofthe barrier metal film is completed; and oxygen plasma generation meanswhich converts the atmosphere within the chamber into a plasma togenerate an oxygen gas plasma so that an oxide layer is formed on themost superficial layer of the barrier metal film.
 19. A barrier metalfilm production apparatus, comprising: a chamber accommodating asubstrate; a metallic etched member provided in the chamber at aposition opposed to the substrate; source gas supply means for supplyinga source gas containing a halogen into the chamber; plasma generationmeans which converts an atmosphere within the chamber into a plasma togenerate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas; excitation means forexciting a gas containing nitrogen in a manner isolated from thechamber; formation means for forming a metal nitride upon reactionbetween nitrogen excited by the excitation means and the precursor;control means which makes a temperature of the substrate lower than atemperature of the formation means to form the metal nitride as a filmon the substrate, and after film formation of the metal nitride, stopssupply of the nitrogen-containing gas and makes the temperature of thesubstrate lower than a temperature of the etched member, thereby formingthe metal component of the precursor as a film on the metal nitride onthe substrate for use as a barrier metal film; oxygen gas supply meansfor supplying an oxygen gas into the chamber immediately beforeformation of the most superficial layer of the barrier metal film iscompleted; and oxygen plasma generation means which converts theatmosphere within the chamber into a plasma to generate an oxygen gasplasma so that an oxide layer is formed on the most superficial layer ofthe barrier metal film.
 20. The barrier metal film production apparatusof any one of claims 14 to 19, further comprising: hydrogen gas supplymeans for supplying a hydrogen gas into the chamber; and hydroxyl groupplasma generation means which converts the atmosphere within the chamberinto a plasma to generate a hydrogen gas plasma so that hydroxyl groupsare formed on the oxide layer.
 21. The barrier metal film productionapparatus of any one of claims 13 to 20, wherein the source gascontaining the halogen is the source gas containing chlorine.
 22. Thebarrier metal film production apparatus of any one of claims 13 to 21,wherein the gas containing nitrogen is a gas containing ammonia.
 23. Thebarrier metal film production apparatus of any one of claims 13 to 22,wherein the etched member is made of tantalum, tungsten, titanium orsilicon which is a halide-forming metal.
 24. A barrier metal filmproduction method comprising: supplying a source gas containing ahalogen and a nitrogen-containing gas to an interior of a chamberbetween a substrate and a metallic etched member; converting anatmosphere within the chamber into a plasma to generate a source gasplasma so that the etched member is etched with the source gas plasma toform a precursor from a metal component contained in the etched memberand the source gas, and also converting the atmosphere within thechamber into a plasma to generate a nitrogen-containing gas plasma sothat a metal nitride is formed upon reaction between nitrogen and theprecursor; making a temperature of the substrate lower than atemperature of plasma generation means to form the metal nitride as abarrier metal film on a surface of the substrate; supplying a diluentgas to a site within the chamber above the surface of the substrate; andperforming a surface treatment which converts the atmosphere within thechamber into a plasma to generate a diluent gas plasma so that nitrogenatoms in a superficial layer of the barrier metal film are removed bythe diluent gas plasma to decrease a nitrogen content of the superficiallayer relative to an interior of a matrix of the barrier metal film. 25.The barrier metal film production method of claim 24, furthercomprising: supplying an oxygen gas into the chamber immediately beforeformation of the most superficial layer of the barrier metal film iscompleted; and converting the atmosphere within the chamber into aplasma to generate an oxygen gas plasma so that an oxide layer is formedon the most superficial layer of the barrier metal film.
 26. A barriermetal film production method comprising: supplying a source gascontaining a halogen and a nitrogen-containing gas to an interior of achamber between a substrate and a metallic etched member; converting anatmosphere within the chamber into a plasma to generate a source gasplasma so that the etched member is etched with the source gas plasma toform a precursor from a metal component contained in the etched memberand the source gas, and also converting the atmosphere within thechamber into a plasma to generate a nitrogen-containing gas plasma sothat a metal nitride is formed upon reaction between nitrogen and theprecursor; making a temperature of the substrate lower than atemperature of plasma generation means to form the metal nitride as abarrier metal film on a surface of the substrate; supplying an oxygengas to a site above the surface of the substrate; and performing asurface treatment which converts the atmosphere within the chamber intoa plasma to generate an oxygen gas plasma so that nitrogen atoms in asuperficial layer of the barrier metal film are removed by the oxygengas plasma to decrease a nitrogen content of the superficial layerrelative to an interior of a matrix of the barrier metal film, whileforming an oxide layer on the most superficial layer of the barriermetal film.
 27. A barrier metal film production method comprising:supplying a source gas containing a halogen and a nitrogen-containinggas to an interior of a chamber between a substrate and a metallicetched member; converting an atmosphere within the chamber into a plasmato generate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and also convertingthe atmosphere within the chamber into a plasma to generate anitrogen-containing gas plasma so that a metal nitride is formed uponreaction between nitrogen and the precursor; making a temperature of thesubstrate lower than a temperature of plasma generation means to formthe metal nitride as a film on a surface of the substrate for use as abarrier metal film; supplying an oxygen gas into the chamber immediatelybefore formation of the most superficial layer of the barrier metal filmis completed; and converting the atmosphere within the chamber into aplasma to generate an oxygen gas plasma so that an oxide layer is formedon the most superficial layer of the barrier metal film.
 28. A barriermetal film production method comprising: supplying a source gascontaining a halogen and a nitrogen-containing gas to an interior of achamber between a substrate and a metallic etched member; converting anatmosphere within the chamber into a plasma to generate a source gasplasma so that the etched member is etched with the source gas plasma toform a precursor from a metal component contained in the etched memberand the source gas, and also converting the atmosphere within thechamber into a plasma to generate a nitrogen-containing gas plasma sothat a metal nitride is formed upon reaction between nitrogen and theprecursor; making a temperature of the substrate lower than atemperature of plasma generation means to form the metal nitride as afilm on a surface of the substrate, then making the temperature of thesubstrate lower than the temperature of the plasma generation means andstopping supply of the gas containing nitrogen, thereby forming themetal component of the precursor as a film on the metal nitride for useas a barrier metal film; supplying an oxygen gas into the chamberimmediately before formation of the most superficial layer of thebarrier metal film is completed; and converting the atmosphere withinthe chamber into a plasma to generate an oxygen gas plasma so that anoxide layer is formed on the most superficial layer of the barrier metalfilm.
 29. A barrier metal film production method comprising: supplying asource gas containing a halogen and a nitrogen-containing gas to aninterior of a chamber between a substrate and a metallic etched member;converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas, and also exciting the gas containingnitrogen in a manner isolated from the chamber accommodating thesubstrate; forming a metal nitride upon reaction between excitednitrogen and the precursor; making a temperature of the substrate lowerthan a temperature of means for formation of the metal nitride to formthe metal nitride as a film on the substrate for use as a barrier metalfilm; supplying an oxygen gas at a site above a surface of the substrateimmediately before formation of the most superficial layer of thebarrier metal film is completed; and converting the atmosphere withinthe chamber into a plasma to generate an oxygen gas plasma so that anoxide layer is formed on the most superficial layer of the barrier metalfilm.
 30. A barrier metal film production method comprising: supplying asource gas containing a halogen and a nitrogen-containing gas to aninterior of a chamber between a substrate and a metallic etched member;converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas, and also exciting the gas containingnitrogen in a manner isolated from the chamber accommodating thesubstrate; forming a metal nitride upon reaction between excitednitrogen and the precursor; making a temperature of the substrate lowerthan a temperature of means for formation of the metal nitride to formthe metal nitride as a film on the substrate, and after film formationof the metal nitride, stopping supply of the nitrogen-containing gas andmaking the temperature of the substrate lower than a temperature of theetched member, thereby forming the metal component of the precursor as afilm on the metal nitride on the substrate for use as a barrier metalfilm; supplying an oxygen gas at a site above a surface of the substrateimmediately before formation of the most superficial layer of thebarrier metal film is completed; and converting the atmosphere withinthe chamber into a plasma to generate an oxygen gas plasma so that anoxide layer is formed on the most superficial layer of the barrier metalfilm.
 31. The barrier metal film production method of any one of claims25 to 30, further comprising: supplying a hydrogen gas into the chamber;and converting the atmosphere within the chamber into a plasma togenerate a hydrogen gas plasma so that hydroxyl groups are formed on theoxide layer.
 32. The barrier metal film production method of any one ofclaims 24 to 31, wherein the source gas containing the halogen is thesource gas containing chlorine.
 33. The barrier metal film productionmethod of any one of claims 24 to 32, wherein the gas containingnitrogen is a gas containing ammonia.
 34. The barrier metal filmproduction method of any one of claims 24 to 33, wherein the etchedmember is made of tantalum, tungsten, titanium or silicon which is ahalide-forming metal.
 35. A metal film production method involvingtreatment of a surface of a substrate having a barrier metal film of ametal nitride formed thereon, comprising: performing a surface treatmentwhich removes nitrogen atoms in a superficial layer of the barrier metalfilm to decrease a nitrogen content of the superficial layer relative toan interior of a matrix of the barrier metal film, thereby substantiallyforming a metal layer on the superficial layer.
 36. A metal filmcomprising a metal layer substantially formed on a superficial layer ofa barrier metal film of a metal nitride formed on a surface of asubstrate, said metal layer being formed by performing a surfacetreatment which removes nitrogen atoms in the superficial layer of thebarrier metal film to decrease a nitrogen content of the superficiallayer relative to an interior of a matrix of the barrier metal film. 37.A metal film production method involving treatment of a surface of asubstrate having a barrier metal film of a metal nitride formed thereon,comprising: performing a surface treatment which etches the barriermetal film on the surface of the substrate with a diluent gas plasma toflatten the barrier metal film.
 38. A metal film production methodinvolving treatment of a surface of a substrate having a barrier metalfilm of a metal nitride formed thereon, comprising: performing a surfacetreatment which etches the barrier metal film on the surface of thesubstrate with a diluent gas plasma to flatten the barrier metal film,and removes nitrogen atoms in a superficial layer of the barrier metalfilm by the diluent gas plasma to decrease a nitrogen content of thesuperficial layer relative to an interior of a matrix of the barriermetal film.
 39. A metal film production method comprising: supplying asource gas containing a halogen to an interior of a chamber between asubstrate and a metallic etched member; converting an atmosphere withinthe chamber into a plasma to generate a source gas plasma so that theetched member is etched with the source gas plasma to form a precursorfrom a metal component contained in the etched member and the sourcegas, and also exciting a gas containing nitrogen in a manner isolatedfrom the chamber accommodating the substrate; forming a metal nitrideupon reaction between excited nitrogen and the precursor; making atemperature of the substrate lower than a temperature of means forformation of the metal nitride to form the metal nitride as a film onthe substrate for use as a barrier metal film; and performing a surfacetreatment which etches the barrier metal film on a surface of thesubstrate with a diluent gas plasma to flatten the barrier metal film.40. A metal film production method comprising: supplying a source gascontaining a halogen to an interior of a chamber between a substrate anda metallic etched member; converting an atmosphere within the chamberinto a plasma to generate a source gas plasma so that the etched memberis etched with the source gas plasma to form a precursor from a metalcomponent contained in the etched member and the source gas, and alsoexciting a gas containing nitrogen in a manner isolated from the chamberaccommodating the substrate; forming a metal nitride upon reactionbetween excited nitrogen and the precursor; making a temperature of thesubstrate lower than a temperature of means for formation of the metalnitride to form the metal nitride as a film on the substrate for use asa barrier metal film; and performing a surface treatment which etchesthe barrier metal film on a surface of the substrate with a diluent gasplasma to flatten the barrier metal film, and removes nitrogen atoms ina superficial layer of the barrier metal film by the diluent gas plasmato decrease a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film.
 41. A metal filmproduction method comprising: performing a surface treatment whichgenerates a diluent gas plasma within a chamber accommodating asubstrate having a barrier metal film of a metal nitride formed thereon,to etch the barrier metal film on a surface of the substrate with thediluent gas plasma, thereby flattening the barrier metal film; thensupplying a source gas containing a halogen into the chamber; convertingan atmosphere within the chamber into a plasma to generate a source gasplasma so that an etched member made of a metal is etched with thesource gas plasma to form a precursor within the chamber from a metalcomponent contained in the etched member and the source gas; and makinga temperature of the substrate lower than a temperature of the etchedmember to form the metal component of the precursor as a film on thesubstrate having the barrier metal film flattened.
 42. A metal filmproduction method comprising: performing a surface treatment whichgenerates a diluent gas plasma within a chamber accommodating asubstrate having a barrier metal film of a metal nitride formed thereon,to etch the barrier metal film on a surface of the substrate with thediluent gas plasma, thereby flattening the barrier metal film, andremoves nitrogen atoms in a superficial layer of the barrier metal filmby the diluent gas plasma to decrease a nitrogen content of thesuperficial layer relative to an interior of a matrix of the barriermetal film; then supplying a source gas containing a halogen into thechamber; converting an atmosphere within the chamber into a plasma togenerate a source gas plasma so that an etched member made of a metal isetched with the source gas plasma to form a precursor within the chamberfrom a metal component contained in the etched member and the sourcegas; and making a temperature of the substrate lower than a temperatureof the etched member to form the metal component of the precursor as afilm on the substrate having the barrier metal film flattened and havingthe nitrogen content of the superficial layer relatively decreased. 43.The metal film production method of claim 37, 39 or 41, furthercomprising: applying a densification treatment for densifying metalatoms in a superficial layer of the barrier metal film after flatteningthe barrier metal film and also relatively decreasing the nitrogencontent of the superficial layer.
 44. The metal film production methodof any one of claims 37 to 43, wherein the diluent gas plasma is anargon gas plasma.
 45. The metal film production method of any one ofclaims 37 to 44, wherein the metal nitride is tantalum nitride, tungstennitride or titanium nitride.
 46. A metal film production apparatus,comprising: a chamber accommodating a substrate; a metallic etchedmember provided in the chamber at a position opposed to the substrate;halogen gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember; barrier plasma generation means which converts an atmospherewithin the chamber into a plasma to generate a source gas plasma so thatthe etched member is etched with the source gas plasma to form aprecursor from a metal component contained in the etched member and thesource gas; excitation means for exciting a gas containing nitrogen in amanner isolated from the chamber; formation means for forming a metalnitride upon reaction between nitrogen excited by the excitation meansand the precursor; control means which makes a temperature of thesubstrate lower than a temperature of the formation means to form themetal nitride as a film on the substrate for use as a barrier metalfilm; diluent gas supply means for supplying a diluent gas to a siteabove a surface of the substrate; and surface treatment plasmageneration means which converts the atmosphere within the chamber into aplasma to generate a diluent gas plasma so that the barrier metal filmon the surface of the substrate is etched with the diluent gas plasma toflatten the barrier metal film.
 47. A metal film production apparatus,comprising: a chamber accommodating a substrate; a metallic etchedmember provided in the chamber at a position opposed to the substrate;halogen gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember; barrier plasma generation means which converts an atmospherewithin the chamber into a plasma to generate a source gas plasma so thatthe etched member is etched with the source gas plasma to form aprecursor from a metal component contained in the etched member and thesource gas; excitation means for exciting a gas containing nitrogen in amanner isolated from the chamber; formation means for forming a metalnitride upon reaction between nitrogen excited by the excitation meansand the precursor; control means which makes a temperature of thesubstrate lower than a temperature of the formation means to form themetal nitride as a film on the substrate for use as a barrier metalfilm; diluent gas supply means for supplying a diluent gas to a siteabove a surface of the substrate; and surface treatment plasmageneration means for performing a surface treatment which converts theatmosphere within the chamber into a plasma to generate a diluent gasplasma so that the barrier metal film on the surface of the substrate isetched with the diluent gas plasma to flatten the barrier metal film,and removes nitrogen atoms in a superficial layer of the barrier metalfilm to decrease a nitrogen content of the superficial layer relative toan interior of a matrix of the barrier metal film.
 48. A metal filmproduction apparatus, comprising: a chamber accommodating a substratehaving a barrier metal film of a metal nitride formed thereon; diluentgas supply means for supplying a diluent gas to an interior of thechamber above a surface of the substrate; surface treatment plasmageneration means which converts an atmosphere within the chamber into aplasma to generate a diluent gas plasma so that the barrier metal filmon the surface of the substrate is etched with the diluent gas plasma toflatten the barrier metal film; a metallic etched member provided in thechamber; source gas supply means for supplying a source gas containing ahalogen to an interior of the chamber between the substrate and theetched member; plasma generation means which converts the source gascontaining the halogen into a plasma to generate a source gas plasma sothat the etched member is etched with the source gas plasma to form aprecursor from a metal component contained in the etched member and thesource gas; and control means which makes a temperature of the substratelower than a temperature of the etched member to form the metalcomponent of the precursor as a film on the flattened barrier metalfilm.
 49. A metal film production apparatus, comprising: a chamberaccommodating a substrate having a barrier metal film of a metal nitrideformed thereon; diluent gas supply means for supplying a diluent gas toan interior of the chamber above a surface of the substrate; surfacetreatment plasma generation means which converts an atmosphere withinthe chamber into a plasma to generate a diluent gas plasma so that thebarrier metal film on the surface of the substrate is etched with thediluent gas plasma to flatten the barrier metal film, and also removesnitrogen atoms in a superficial layer of the barrier metal film by thediluent gas plasma to decrease a nitrogen content of the superficiallayer relative to an interior of a matrix of the barrier metal film; ametallic etched member provided in the chamber; source gas supply meansfor supplying a source gas containing a halogen to an interior of thechamber between the substrate and the etched member; plasma generationmeans which converts the source gas containing the halogen into a plasmato generate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas; and control meanswhich makes a temperature of the substrate lower than a temperature ofthe etched member to form the metal component of the precursor as a filmon the barrier metal film flattened and having the nitrogen content ofthe superficial layer relatively decreased.
 50. The metal filmproduction apparatus of claim 47 or 49, further comprising:densification treatment means for densifying metal atoms in thesuperficial layer after flattening the barrier metal film and alsorelatively decreasing the nitrogen content of the superficial layer. 51.The metal film production apparatus of any one of claims 46 to 50,wherein the diluent gas plasma is an argon gas plasma.
 52. The metalfilm production apparatus of any one of claims 46 to 51, wherein themetal nitride is tantalum nitride, tungsten nitride or titanium nitride.53. A metal film formed by flattening a barrier metal film of a metalnitride on a surface of a substrate by etching with a diluent gasplasma.
 54. A metal film formed by a surface treatment which flattens abarrier metal film of a metal nitride on a surface of a substrate byetching with a diluent gas plasma, and removes nitrogen atoms in asuperficial layer of the barrier metal film by the diluent gas plasma todecrease a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film.
 55. A metal filmproduction method involving treatment of a surface of a substrate havinga barrier metal film of a metal nitride formed thereon, comprising:performing a surface treatment which reacts the barrier metal film onthe surface of the substrate in a reducing gas atmosphere to removenitrogen atoms in a superficial layer of the barrier metal film, therebydecreasing a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film.
 56. A metal filmproduction method comprising: supplying a source gas containing ahalogen to an interior of a chamber between a substrate and a metallicetched member; converting an atmosphere within the chamber into a plasmato generate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and also exciting agas containing nitrogen in a manner isolated from the chamberaccommodating the substrate; forming a metal nitride upon reactionbetween excited nitrogen and the precursor; making a temperature of thesubstrate lower than a temperature of means for formation of the metalnitride to form the metal nitride as a film on the substrate for use asa barrier metal film; and performing a surface treatment which reactsthe barrier metal film on a surface of the substrate in a reducing gasatmosphere to remove nitrogen atoms in a superficial layer of thebarrier metal film, thereby decreasing a nitrogen content of thesuperficial layer relative to an interior of a matrix of the barriermetal film.
 57. A metal film production method comprising: performing asurface treatment in a chamber accommodating a substrate having abarrier metal film of a metal nitride formed thereon, said surfacetreatment comprising reacting the barrier metal film on a surface of thesubstrate in a reducing gas atmosphere to remove nitrogen atoms in asuperficial layer of the barrier metal film, thereby decreasing anitrogen content of the superficial layer relative to an interior of amatrix of the barrier metal film; then supplying a source gas containinga halogen into the chamber; converting an atmosphere within the chamberinto a plasma to generate a source gas plasma so that a metallic etchedmember is etched with the source gas plasma to form a precursor withinthe chamber from a metal component contained in the etched member andthe source gas; and making a temperature of the substrate lower than atemperature of the etched member to form the metal component of theprecursor as a film on the substrate having the barrier metal filmflattened thereon.
 58. The metal film production method of any one ofclaims 55 to 57, wherein the reducing gas atmosphere is a hydrogen gasplasma.
 59. The metal film production method of any one of claims 55 to58, wherein the metal nitride is tantalum nitride, tungsten nitride, ortitanium nitride.
 60. A metal film production apparatus, comprising: achamber accommodating a substrate; a metallic etched member provided inthe chamber at a position opposed to the substrate; halogen gas supplymeans for supplying a source gas containing a halogen to an interior ofthe chamber between the substrate and the etched member; barrier plasmageneration means which converts an atmosphere within the chamber into aplasma to generate a source gas plasma so that the etched member isetched with the source gas plasma to form a precursor from a metalcomponent contained in the etched member and the source gas; excitationmeans for exciting a gas containing nitrogen in a manner isolated fromthe chamber; formation means for forming a metal nitride upon reactionbetween nitrogen excited by the excitation means and the precursor;control means which makes a temperature of the substrate lower than atemperature of the formation means to form the metal nitride as a filmon the substrate for use as a barrier metal film; reducing gas supplymeans for supplying a reducing gas to a site above a surface of thesubstrate; and surface treatment means which reacts the barrier metalfilm on the surface of the substrate in a reducing gas atmosphere toremove nitrogen atoms in a superficial layer of the barrier metal film,thereby decreasing a nitrogen content of the superficial layer relativeto an interior of a matrix of the barrier metal film.
 61. A metal filmproduction apparatus, comprising: a chamber accommodating a substratehaving a barrier metal film of a metal nitride formed thereon; reducinggas supply means for supplying a reducing gas to a site above a surfaceof the substrate; surface treatment means which reacts the barrier metalfilm on the surface of the substrate in a reducing gas atmosphere toremove nitrogen atoms in a superficial layer of the barrier metal film,thereby decreasing a nitrogen content of the superficial layer relativeto an interior of a matrix of the barrier metal film; a metallic etchedmember provided in the chamber; source gas supply means for supplying asource gas containing a halogen to an interior of the chamber betweenthe substrate and the etched member; plasma generation means whichconverts the source gas containing the halogen into a plasma to generatea source gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas; and control means which makes atemperature of the substrate lower than a temperature of the etchedmember to form the metal component of the precursor as a film on thebarrier metal film having the nitrogen content of the superficial layerrelatively decreased.
 62. The metal film production apparatus of claim60 or 61, wherein the reducing gas supply means is means for supplying agas containing hydrogen, and the surface treatment means is hydrogen gasplasma generation means for generating a hydrogen gas plasma.
 63. Themetal film production apparatus of any one of claims 60 to 62, whereinthe metal nitride is tantalum nitride, tungsten nitride, or titaniumnitride.
 64. A metal film formed by a surface treatment which reacts abarrier metal film of a metal nitride on a surface of a substrate in areducing gas atmosphere to remove nitrogen atoms in a superficial layerof the barrier metal film, thereby decreasing a nitrogen content of thesuperficial layer relative to an interior of a matrix of the barriermetal film.
 65. A metal film production method involving treatment of asurface of a substrate having a barrier metal film of a metal nitrideformed thereon, comprising: performing a surface treatment which formsnuclei of silicon atoms on a surface of the barrier metal film on thesurface of the substrate by a gas plasma containing silicon.
 66. A metalfilm production method comprising: supplying a source gas containing ahalogen to an interior of a chamber between a substrate and a metallicetched member; converting an atmosphere within the chamber into a plasmato generate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas, and also exciting agas containing nitrogen in a manner isolated from the chamberaccommodating the substrate; forming a metal nitride upon reactionbetween excited nitrogen and the precursor; making a temperature of thesubstrate lower than a temperature of means for formation of the metalnitride to form the metal nitride as a film on the substrate for use asa barrier metal film; and performing a surface treatment which formsnuclei of silicon atoms on a surface of the barrier metal film on asurface of the substrate by a gas plasma containing silicon.
 67. A metalfilm production method comprising: performing a surface treatment in achamber accommodating a substrate having a barrier metal film of a metalnitride formed thereon, said surface treatment comprising forming nucleiof silicon atoms on a surface of the barrier metal film on a surface ofthe substrate by a gas plasma containing silicon; then supplying asource gas containing a halogen into the chamber; converting anatmosphere within the chamber into a plasma to generate a source gasplasma so that a metallic etched member is etched with the source gasplasma to form a precursor within the chamber from a metal componentcontained in the etched member and the source gas; and making atemperature of the substrate lower than a temperature of the etchedmember to form the metal component of the precursor as a film on thesubstrate having the nuclei of silicon atoms formed on the surface ofthe barrier metal film.
 68. The metal film production method of any oneof claims 65 to 67, wherein the gas containing silicon is a silane. 69.The metal film production method of anyone of claims 65 to 68, whereinthe metal nitride is tantalum nitride, tungsten nitride, or titaniumnitride.
 70. A metal film production apparatus, comprising: a chamberaccommodating a substrate; a metallic etched member provided in thechamber at a position opposed to the substrate; halogen gas supply meansfor supplying a source gas containing a halogen to an interior of thechamber between the substrate and the etched member; barrier plasmageneration means which converts an atmosphere within the chamber into aplasma to generate a source gas plasma so that the etched member isetched with the source gas plasma to form a precursor from a metalcomponent contained in the etched member and the source gas; excitationmeans for exciting a gas containing nitrogen in a manner isolated fromthe chamber; formation means for forming a metal nitride upon reactionbetween nitrogen excited by the excitation means and the precursor;control means which makes a temperature of the substrate lower than atemperature of the formation means to form the metal nitride as a filmon the substrate for use as a barrier metal film; silicon-containing gassupply means for supplying a gas containing silicon to a site above asurface of the substrate; and surface treatment plasma generation meanswhich generates a gas plasma containing silicon to form nuclei ofsilicon atoms on a surface of the barrier metal film on the surface ofthe substrate.
 71. A metal film production apparatus, comprising: achamber accommodating a substrate having a barrier metal film of a metalnitride formed thereon; silicon-containing gas supply means forsupplying a gas containing silicon to a site above a surface of thesubstrate; surface treatment plasma generation means which generates agas plasma containing silicon to form nuclei of silicon atoms on asurface of the barrier metal film on the surface of the substrate; ametallic etched member provided in the chamber; source gas supply meansfor supplying a source gas containing a halogen to an interior of thechamber between the substrate and the etched member; plasma generationmeans which converts the source gas containing the halogen into a plasmato generate a source gas plasma so that the etched member is etched withthe source gas plasma to form a precursor from a metal componentcontained in the etched member and the source gas; and control meanswhich makes a temperature of the substrate lower than a temperature ofthe etched member to form the metal component of the precursor as a filmon the barrier metal film having the nuclei of silicon atoms formed onthe surface thereof.
 72. The metal film production apparatus of claim 70or 71, wherein the gas containing silicon is a silane.
 73. The metalfilm production apparatus of any one of claims 70 to 72, wherein themetal nitride is tantalum nitride, tungsten nitride, or titaniumnitride.
 74. A metal film formed by applying a surface treatment to abarrier metal film of a metal nitride on a surface of a substrate suchthat nuclei of silicon atoms are formed on a surface of the barriermetal film on the surface of the substrate by a gas plasma containingsilicon.